Method for producing thermoplastic elastomers

ABSTRACT

Thermoplastic elastomers can be prepared by (co)polymerization of monomers from the group consisting of C 2 -C 8 -α-olefins, C 4 -C 15 -diolefins and other monomers in the bulk, solution, slurry or gas phase, the catalysts employed being metallocene compounds or the π complex compounds of the formulae                    
     in which 
     CpI and CpII represent carbanions having a cyclopentadienyl-containing structure, 
     πI and πII represent charged or electrically neutral π systems, 
     D represents a donor atom and 
     A represents an acceptor atom, 
     where D and A are linked by a reversible coordinate bond such that the donor group assumes a positive (part) charge and the acceptor group assumes a negative (part) charge, 
     M represents a transition metal of sub-group III, IV, V or VI of the Periodic Table of the Elements (Mendeleev), including the lanthanides and actinides, 
     X denotes one anion equivalent and 
     n denotes the number zero, one, two, three or four, depending on the charge of M.

FIELD OF THE INVENTION

The present invention relates to the use of π systems or of metallocenecompounds in which a transition metal with two π systems, and inparticular with aromatic π systems, such as anionic cyclopentadienylligands (carbanions) is complexed and the two systems are bondedreversibly to one another by at least one bridge of a donor and anacceptor, as organometallic catalysts in a process for the preparationof thermoplastic elastomers by (co)polymerization of monomers from thegroup consisting of C₂-C₈-α-olefins, C₄-C₁₅-diolefins, mono- ordihalogenated diolefins, vinyl esters, (meth)acrylates and styrene. Thecoordinate bond forming between the donor atom and the acceptor atomproduces a positive (part) charge in the donor group and a negative(part) charge in the acceptor group:

BACKGROUND OF THE INVENTION

Metallocenes and their use as catalysts in the polymerization of olefinshave been known for a long time (EP-A 129 368 and the literature citedtherein). It is furthermore known from EP-A '368 that metallocenes incombination with aluminum-alkyl/water as cocatalysts are active systemsfor the polymerization of ethylene (thus, for example,methylaluminoxane=MAO is formed from 1 mol of trimethylaluminum and 1mol of water. Other stoichiometric ratios have also already been usedsuccessfully (WO 94/20506)). Metallocenes in which the cyclopentadienylskeletons are linked to one another covalently via a bridge are alsoalready known. An example of the numerous patents and applications inthis field which may be mentioned is EP-A 704 461, in which the linkagegroup mentioned therein is a (substituted) methylene group or ethylenegroup, a silylene group, a substituted silylene group, a substitutedgermylene group or a substituted phosphine group. The bridgedmetallocenes are also envisaged as polymerization catalysts for olefinsin EP '461. In spite of the numerous patents and applications in thisfield, there continues to be a demand for improved catalysts which aredistinguished by a high activity, so that the amount of catalystremaining in the polymer can be set to a low level, and which areequally suitable for the polymerization and copolymerization of olefinsto give thermoplastics and to give elastomeric products and also for thepolymerization and copolymerization of diolefins, optionally witholefins.

SUMMARY OF THE INVENTION

It has now been found that particularly advantageous catalysts can beprepared from bridged π complex compounds, and in particular frommetallocene compounds, in which the bridging of the two π systems isestablished by one, two or three reversible donor-acceptor bonds, inwhich in each case a coordinate or so-called dative bond which isoverlapped at least formally by an ionic bond forms between the donoratom and the acceptor atom, and in which one of the donor or acceptoratoms can be part of the particular associated π system. Thereversibility of the donor-acceptor bond also allows, in addition to thebridged state identified by the arrow between D and A, the non-bridgedstate in which the two π systems can rotate against one another, forexample by an angle of 360°, as a result of their inherent rotationalenergy, without the integrity of the metal complex being surrendered.When the rotation is complete, the donor-acceptor bond “snaps in” again.If several donors and/or acceptors are present, such “snapping in” canalready take place after angles of less than 360° have been passedthrough. π systems according to the invention which are to be employed,for example metallocenes, can therefore be represented merely by adouble arrow and the formula parts (Ia) and (Ib) or (XIIIa) and (XIIIb)to include both states.

DETAILED DESCRIPTION OF THE INVENTION

The invention accordingly relates to a process for the preparation ofthermoplastic elastomers by (co)polymerization of monomers from thegroup consisting of C₂-C₈-α-olefins, C₄-C₁₅-diolefins, mono- ordihalogenated C₄-C₁₅-diolefins, vinyl esters, (meth)acrylates andstyrene in the bulk, solution, slurry or gas phase in the presence oforganometallic catalysts, which can be activated by cocatalysts, whichcomprises employing as the organometallic catalysts metallocenecompounds of the formula

in which

CpI CpII are two identical or different carbanions having acyclopentadienyl-containing structure, in which one to all the H atomscan be replaced by identical or different radicals from the groupconsisting of linear or branched C₁-C₂₀-alkyl, which can bemonosubstituted to completely substituted by halogen, mono- totrisubstituted by phenyl and mono- to trisubstituted by vinyl,C₆-C₁₂-aryl, halogenoaryl having 6 to 12 C atoms, organometalsubstituents, such as silyl, trimethylsilyl or ferrocenyl, and 1 or 2can be replaced by D and A,

D denotes a donor atom, which can additionally carry substituents andhas at least one free electron pair in its particular bond state,

A denotes an acceptor atom, which can additionally carry substituentsand has an electron pair gap in its particular bond state,

where D and A are linked by a reversible coordinate bond such that thedonor group assumes a positive (part) charge and the acceptor groupassumes a negative (part) charge,

M represents a transition metal of sub-group III, IV, V or VI of thePeriodic Table of the Elements (Mendeleev), including the lanthanidesand actinides,

X denotes one anion equivalent and

n denotes the number zero, one, two, three or four, depending on thecharge of M, or π complex compounds, and in particular metallocenecompounds of the formula

 in which

πI and πII represent different charged or electrically neutral π systemswhich can be condensed with one or two unsaturated or saturated five- orsix-membered rings,

D denotes a donor atom, which is a substituent of πI or part of the πsystem of πI and has at least one free electron pair in its particularbond state,

A denotes an acceptor atom, which is a substituent of πII or part of theπ system of πII and has an electron pair gap in its particular bondstate,

where D and A are linked by a reversible coordinate bond such that thedonor group assumes a positive (part) charge and the acceptor groupassumes a negative (part) charge, and where at least one of D and A ispart of the particular associated π system,

where D and A in their turn can carry substituents,

where each π system and each fused-on ring system can contain one ormore D or A or D and A and

wherein πI and πII in the non-fused or in the fused form, one to all theH atoms of the π system independently of one another can be replaced byidentical or different radicals from the group consisting of linear orbranched C₁-C₂₀-alkyl, which can be monosubstituted to completelysubstituted by halogen, mono- to trisubstituted by phenyl or mono- totrisubstituted by vinyl, C₆-C₁₂-aryl, halogenoaryl having 6 to 12 Catoms, organometal substituents, such as silyl, trimethylsilyl orferrocenyl, or one or two can be replaced by D and A, so that thereversible coordinate D→A bond is formed (i) between D and A, which areboth parts of the particular π system or the fused-on ring system, or(ii) of which D or A is (are) part of the π system or of the fused-onring system and in each case the other is (are) a substituent of thenon-fused π system or the fused-on ring system,

M and X have the above meaning and

n denotes the number zero, one, two, three or four, depending on thecharges of M and those of π-I and π-II.

π systems according to the invention are substituted and unsubstitutedethylene, allyl, pentadienyl, benzyl, butadiene, benzene, thecyclopentadienyl anion and the species which result by replacement of atleast one C atom by a heteroatom. Among the species mentioned, thecyclic species are preferred. The nature of the coordination of suchligands (π systems) to the metal can be of the σ type or of the π type.

Such metallocene compounds of the formula (I) which are to be employedaccording to the invention can be prepared by reacting with one anothereither in each case a compound of the formulae (II) and (III)

or in each case a compound of the formulae (IV) and (V)

or in each case a compound of the formulae (VI) and (VII)

with elimination of M′X, in the presence of an aprotic solvent, or ineach case a compound of the formulae (VIII) and (III)

or in each case a compound of the formulae (IV) and (IX)

or in each case a compound of the formulae (X) and (VII)

with elimination of E(R¹R²R³)X and F(R⁴R⁵R⁶)X, in the absence or in thepresence of an aprotic solvent, where

CpI, CpII, D, A, M, X and n have the above meaning,

CpIII and CpIV represent two identical or different non-chargedmolecular parts having a cyclopentadiene-containing structure, but areotherwise the same as CpI and CpII,

M′ denotes one cation equivalent of an alkali metal or alkaline earthmetal or Tl,

E and F independently of one another denote one of the elements Si, Geor Sn and

R¹, R², R³, R⁴, R⁵ and R⁶ independently of one another representstraight-chain or branched C₁-C₂₀-alkyl, C₆-C₁₂-aryl,C₁-C₆-alkyl-C₆-C₁₂-aryl, C₆-C₁₂-aryl-C₁-C₆-alkyl, vinyl, allyl orhalogen,

and where furthermore, in the formulae (VIII), (IX) and (X), hydrogencan replace E(R¹R²R³) and F(R⁴R⁵R⁶), and in this case X can alsorepresent an amide anion of the type R₂N⁻ or a carbanion of the typeR₃C⁻ or an alcoholate anion of the type RO⁻, and where furthermore it ispossible to react compounds of the formula (II) or (VIII) directly witha transition metal compound of the formula (VII) in the presence ofcompounds of the formula (V) or (IX).

In the reaction of (VIII) with (III) or (IV) with (IX) or (X) with(VII), in the case of the variant mentioned last, the structure (I)forms with elimination of amine R₂NH or R₂NE(R¹R²R³) or R₂NF(R⁴R⁵R⁶) ora hydrocarbon compound of the formula R₃CH or R₃CE(R¹R²R³) orR₃CF(R⁴R⁵R⁶) or an ether ROE(R¹R²R³) or ROF(R⁴R⁵R⁶), in which theorganic radicals R are identical or different and independently of oneanother are C₁-C₂₀-alkyl, C₆-C₁₂-aryl, substituted or unsubstitutedallyl, benzyl or hydrogen. Examples of the amine or hydrocarbon, ether,silane, stannane or germane eliminated are, for example, dimethylamine,diethylamine, di-(n-propyl)amine, di-(isopropyl)amine,di-(tert-butyl)amine, tert-butylamine, cyclohexylamine, aniline,methylphenylamine, di-(allyl)amine or methane, toluene,trimethylsilylamine, trimethylsilyl ether, tetramethylsilane and thelike.

It is also possible to react compounds of the formula (II) or (VIII)directly with a transition metal compound of the formula (VII) in thepresence of compounds of the formula (V) or (IX).

π complex compounds of the formula (MIII) in which the π systems arecyclic and aromatic (metallocenes) can be prepared analogously, thefollowing compounds being employed accordingly:

Open-chain π complex compounds are prepared by processes known to theexpert with incorporation of donor and acceptor groups.

The catalysts of the formulae (I) and (XIII) which can be employedaccording to the invention can be present both in monomeric and indimeric or oligomeric form.

According to the invention, the reaction is carried out in the bulk,solution, slurry or gas phase at −60 to 250° C., preferably 0 to +200°C., under 1 to 65 bar, in the presence or absence of saturated oraromatic hydrocarbons or of saturated or aromatic halogenohydrocarbonsand in the presence or absence of hydrogen, the metallocene compounds orthe π complex compounds being employed as catalysts in an amount of 10¹to 10¹² mol of all the monomers per mole of metallocene or the π complexcompounds, and it being furthermore possible to carry out the reactionin the presence of Lewis acids, Bronstedt acids or Pearson acids, oradditionally in the presence of Lewis bases.

Such Lewis acids are, for example, boranes or alanes, such asaluminum-alkyls, aluminum halides, aluminum alcoholates, organoboroncompounds, boron halides, boric acid esters or compounds of boron oraluminum which contain both halide and alkyl or aryl or alcoholatesubstituents, and mixtures thereof, or the triphenylmethyl cation.Aluminoxane or mixtures of aluminum-containing Lewis acids with waterare particularly preferred. According to current knowledge, all theacids act as ionizing agents which form a metallocenium cation, thecharge of which is compensated by a bulky, fully coordinating anion.

According to the invention, the reaction products of such ionizingagents with metallocene compounds of the formula (I) can furthermore beemployed. They can be described by the formulae (XIa) to (XId)

in which

Anion represents the entire bulky, poorly coordinating anion and Baserepresents a Lewis base.

Examples of poorly coordinating anions of this kind are, for example,

B(C₆H₅)₄ ^(⊖), B(C₆F₅)₄ ^(⊖), B(CH₃)(C₆F₅)₃ ^(⊖),

 or sulfonates, such as tosylate or triflate, tetrafluoroborates,hexafluorophosphates or -antimonates, perchlorates, and voluminouscluster molecular anions of the carborane type, for example C₂B₉H₁₂ ^(⊖)or CB₁₁H₁₂ ^(⊖). If such anions are present, metallocene compounds canalso act as highly active polymerization catalysts in the absence ofaluminoxane. This is the case, above all, if one X ligand represents analkyl group, allyl or benzyl. However, it may also be advantageous toemploy such metallocene complexes with voluminous anions in combinationwith aluminum-alkyls, such as (CH₃)₃Al, (C₂H₅)₃Al, (n-/i-propyl)₃Al,(n-/t-butyl)₃Al, (i-butyl)₃Al, the isomeric pentyl-, hexyl- oroctylaluminum-alkyls or lithium-alkyls, such as methyl-Li, benzyl-Li orbutyl-Li, or the corresponding organo-Mg compounds, such as Grignardcompounds, or organo-Zn compounds. Such metal-alkyls on the one handtransfer alkyl groups to the central metal, and on the other handscavenge water or catalyst poisons from the reaction medium or monomerduring polymerization reactions. Metal-alkyls of the type described canalso advantageously be employed in combination with aluminoxanecocatalysts, for example in order to reduce the amount of aluminoxanerequired. Examples of boron compounds with which such anions can beintroduced are:

triethylammonium tetraphenylborate,

tripropylammonium tetraphenylborate,

tri(n-butyl)ammonium tetraphenylborate,

tri(t-butyl)ammonium tetraphenylborate,

N,N-dimethylanilinium tetraphenylborate,

N,N-diethylanilinium tetraphenylborate,

N,N-dimethyl(2,4,6-trimethylanilinium) tetraphenylborate,

trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis-(pentafluorophenyl)borate,

tripropylammonium tetrakis(pentafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,tri(sec-butyl)ammonium

tetrakis(pentafluorophenyl)borate,

N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,N,N-dimethyl(2,4,5-trimethylanilinium)tetrakis(pentafluorophenyl)borate,

trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate and

N,N-dimethyl(2,4,6-trimethylanilinium)tetrakis(2,3,4,6-tetrafluorophenyl)borate;

dialkylammmonium salts, such as:

di(i-propyl)ammonium tetrakis(pentafluorophenyl)borate and

dicyclohexylammoniuni tetrakis(pentafluorophenyl)borate;

tri-substituted phosphonium salts, such as:

triphenylphosphonium tetrakis(pentafluorophenyl)borate,

tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate and

tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate;

tritolylmethyl tetrakis(pentafluorophenyl)borate,

triphenylmethyl tetraphenylborate (trityl tetraphenylborate),

trityl tetrakis(pentafluorophenyl)borate,

silver tetrafluoroborate,

tris(pentafluorophenyl)borane and

tris(trifluoromethyl)borane.

The metallocene compounds to be employed according to the invention andthe π complex compounds can be employed in isolated form as the puresubstances for the (co)polymerization. However, it is also possible toproduce them and use them “in situ” in the (co)polymerization reactor ina manner known to the expert.

The first and the second carbanion CpI and CpII having acyclopentadienyl skeleton can be identical or different. Thecyclopentadienyl skeleton can be, for example, one from the groupconsisting of cyclopentadiene, substituted cyclopentadiene, indene,substituted indene, fluorene and substituted fluorene. 1 to 4substituents may be present per cyclopentadiene or fused-on benzenering. These substituents can be C₁-C₂₀-alkyl, such as methyl, ethyl,propyl, isopropyl, butyl or iso-butyl, hexyl, octyl, decyl, dodecyl,hexadecyl, octadecyl or eicosyl, C₁-C₂₀-alkoxy, such as methoxy, ethoxy,propoxy, isopropoxy, butoxy or iso-butoxy, hexoxy, octyloxy, decyloxy,dodecyloxy, hexadecyloxy, octadecyloxy, eicosyloxy, halogen, such asfluorine, chlorine or bromine, C₆-C₁₂-aryl, such as phenyl,C₁-C₄-alkylphenyl, such as tolyl, ethylphenyl, (i-)propylphenyl, (i-,tert-)butylphenyl or xylyl, halogenophenyl, such as fluoro-, chloro- orbromophenyl, naphthyl or biphenylyl, triorganyl-silyl, such astrimethylsilyl (TMS), ferrocenyl and D or A, as defined above. Fused-onaromatic rings can furthermore be partly or completely hydrogenated, sothat only the double bond of which both the fused-on ring and thecyclopentadiene ring have a portion remains. Benzene rings, such as inindene or fluorene, can furthermore contain one or two further fused-onbenzene rings. The cyclopentadiene or cyclopentadienyl ring and afused-on benzene ring can also furthermore together contain a furtherfused-on benzene ring.

In the form of their anions, such cyclopentadiene skeletons areexcellent ligands for transition metals, each cyclopentadienyl carbanionof the optionally substituted form mentioned compensating a positivecharge of the central metal in the complex. Individual examples of suchcarbanions are cyclopentadienyl, methyl-cyclopentadienyl,1,2-dimethyl-cyclopentadienyl, 1,3-dimethyl-cyclopentadienyt, indenyl,2-phenylindenyl, 2-methyl-indenyl, 2-methyl-4-phenyl-indenyl,2,4,7-trimethyl-indenyl, 1,2-diethyl-cyclopentadienyl,tetramethyl-cyclopentadienyl, ethyl-cyclopentadienyl,n-butyl-cyclopentadienyl, n-octyl-cyclopentadienyl,β-phenylpropyl-cyclopentadienyl, tetrahydroindenyl,propyl-cyclopentadienyl, t-butyl-cyclopentadienyl,benzyl-cyclopentadienyl, diphenylmethyl-cyclopentadienyl,trimethylgermyl-cyclopentadienyl, trimethylstannyl-cyclopentadienyl,trimethyl-stannylcyclopentadienyl, trifluoromethyl-cyclopentadienyl,trimethylsilyl-cyclopentadienyl, pentamethylcyclopentadienyl, fluorenyl,tetrahydro- and octahydro-fluorenyl, fluorenyls and indenyls which arebenzo-fused on the six-membered ring,N,N-dimethylamino-cyclopentadienyl, dimethylphosphinocyclopentadienyl,methoxy-cyclopentadienyl, dimethylboranyl-cyclopentadienyl and(N,N-dimethylaminomethyl)-cyclopentadienyl. For the preparation ofhighly isotactic blocks (sequences), for example,quasi-rac-bis(indenyt)-metallocenes having a D/A bridge which canadditionally carry, for example, alkyl, aryl and/or silyl substituentsor benzo-fused structures, for example in the 2-position or 4-, 5-, 6-,or 7-position, to increase the molecular weight and isotacticity and themelting point, are suitable. However,D/A-bis(cyclopentadienyl)-metallocenes having substitution patterns(3,3′) of comparable symmetry are also possible. D/A-bridged(cyclopentadienyl)(fluorenyl)-metallocenes or else(cyclopentadienyl)(3,4-disubstituted cyclopentadienyl)-metallocenes arecorrespondingly suitable, for example, for the preparation ofsyndiotactic blocks (sequences).

In addition to the first donor-acceptor bond between D and A which isobligatorily present, further donor-acceptor bonds can be formed ifadditional D and/or A are present as substituents of the particularcyclopentadiene systems or substituents or parts of the π systems. Alldonor-acceptor bonds are characterized by their reversibility describedabove. In the case of several D and A, these can occupy variouspositions of those mentioned. The invention accordingly relates both tothe bridged molecular states (Ia) and (XIIIa) and to the non-bridgedstates (Ib) and (XIIIb). The number of D groups can be identical to ordifferent from the number of A groups. Preferably, CpI and CpII or πIand πII are linked via only one donor-acceptor bridge.

In addition to the D/A bridges according to the invention, covalentbridges can also be present. In this case, the D/A bridges intensify thestereorigidity and the heat stability of the catalyst. In changingbetween a closed and open D/A bond, sequence polymers of higher andlower stereoregularity are accessible. Such sequences can have differentchemical compositions in the case of copolymers.

The π complex compounds are likewise characterized by the presence of atleast one coordinate bond between donor atom(s) D and acceptor atom(s)A. Both D and A here can be substituents of their particular π systemsπI and πII or part of the π system, but with always at least one of Dand A being part of the π system. π system here is understood as meaningthe entire π system, which is optionally fused once or twice. Thefollowing embodiments result from this:

D is part of the π system, A is a substituent of the π system;

D is a substituent of the π system, A is part of the it system;

D and A are parts of their particular π system.

The following heterocyclic ring systems in which D or A is part of thering system may be mentioned as examples:

Important heterocyclic ring systems are the systems labeled (a), (b),(c), (d), (g), (m), (n) and (o); those labeled (a), (b), (c) and (m) areparticularly important.

In the case where one of D and A is a substituent of its associated ringsystem, the ring system is 3-, 4-, 5-, 6-, 7- or 8-membered with orwithout an electric charge, and can be further substituted and/or fusedin the manner described. 5- and 6-membered ring systems are preferred.The negatively charged cyclopentadienyl system is particularlypreferred.

The first and the second π system πI and πII respectively, if it isformed as a ring system, can correspond to CpI and CpII respectively inthe case where one of D and A is a substituent of the ring system.

Possible donor groups are, above all, those in which the donor atom D isan element of main group 5, 6 or 7, preferably 5 or 6, of the PeriodicTable of the Elements (Mendeleev) and has at least one free electronpair, and where the donor atom in the case of elements of main group 5is in a bond state with substituents, and in the case of elements ofmain group 6 can be in such a state; donor atoms of main group 7 carryno substituents. This is illustrated by the example of phosphorus P,oxygen O and chlorine Cl as donor atoms as follows, where “Subst.”represents those substituents mentioned and “-Cp” represents the bond tothe cyclopentadienyl-containing carbanion, a line with an arrow has themeaning of a coordinate bond given in formula (I) and other lines denoteelectron pairs present:

Possible acceptor groups are, above all, those in which the acceptoratom A is an element from main group 3 of the Periodic Table of theElements (Mendeleev), such as boron, aluminum, gallium, indium andthallium, is in a bond state with substituents and has an electron gap.

D and A are linked by a coordinate bond, where D assumes a positive(part) charge and A assumes a negative (part) charge.

A distinction is accordingly being made between the donor atom D and thedonor group and between the acceptor atom A and the acceptor group. Thecoordinate bond D→A is established between the donor atom D and theacceptor atom A. The donor group denotes the unit of the donor atom D,the substituents optionally present and the electron pairs present; theacceptor group correspondingly denotes the unit of the acceptor atom A,the substituents and the electron gap present.

The bond between the donor atom or the acceptor atom and thecyclopentadienyl-containing carbanion can be interrupted by spacergroups in the context of D-spacer-Cp or A-spacer-Cp. In the third of theabove formula examples, ═C(R)— represents such a spacer between O andCp. Such spacer groups are, for example: dimethylsilyl, diethylsilyl,di-n-propylsilyl, diisopropylsilyl, di-n-butylsilyl, di-t-butylsilyl,d-n-hexylsilyl, methylphenylsilyl, ethylmethylsilyl, diphenylsilyl,di(p-t-butylphenethylsilyl), n-hexylmethylsilyl, cyclopentamethylsilyl,cyclotetramethylenesilyl, cyclotrimethylenesilyl, dimethylgermanyl,diethylgermanyl, phenyl-amino, t-butylamino, methylamino,t-butylphosphino, ethylphosphino, phenyl-phosphino, methylene,dimethylmethylene (i-propylidene), diethylmethylene, ethylene,dimethylethylene, diethylethylene, dipropylethylene, propylene,dimethylpropylene, diethylpropylene, 1,1-dimethyl-3,3-dimethylpropylene,teramethyldisiloxane, 1,1,4,4-tetramethyldisilylethylene anddiphenylmethylene.

D and A are preferably bonded to the cyclopentadienyl-containingcarbanion without a spacer.

D and A independently of one another can be on the cyclopentadiene (or-dienyl) ring or a fused-on benzene ring or another substituent of CpIand CpII respectively or πI and πII respectively. In the case of severalD and A, these can occupy various positions of those mentioned.

Substituents on the donor atoms N, P, As, Sb, Bi, O, S, Se and Te and onthe acceptor atoms B, Al, Ga, In and Tl are, for example:C₁-C₁₂-(cyclo)alkyl, such as methyl, ethyl, propyl, i-propyl,cyclopropyl, butyl, i-butyl, tert-butyl, cyclobutyl, pentyl, neopentyl,cyclopentyl, hexyl, cyclohexyl and the isomeric heptyls, octyls, nonyls,decyls, undecyls and dodecyls; the C₁-C₁₂-alkoxy groups which correspondto these; vinyl, butenyl and allyl; C₆-C₁₂-aryl, such as phenyl,naphthyl or biphenylyl and benzyl, which can be substituted by halogen,1 or 2 C₁-C₄-alkyl groups, C₁-C₄-alkoxy groups, nitro or halogenoalkylgroups, C₁-C₆-alkyl-carboxyl, C₁-C₆-alkyl-carbonyl or cyano (for exampleperfluorophenyl, m,m′-bis(trifluoromethyl)-phenyl and analogoussubstituents familiar to the expert); analogous aryloxy groups; indenyl;halogen, such as F, Cl, Br and I, 1-thienyl, disubstituted amino, suchas (C₁-C₁₂-alkyl)₂amino, and diphenylamino,(C₁-C₁₂-alkyl)(phenyl)aamino, (C₁-C₁₂-alkylphenyl)amino,tris-(C₁-C₁₂-alkyl)-silyl, NaSO₃-aryl, such as NaSO₃-phenyl andNaSO₃-tolyl, and C₆H₅—C≡C—; aliphatic and aromatic C₁-C₂₀-silyl, thealkyl substituents of which can additionally be octyl, decyl, dodecyl,stearyl or eicosyl, in addition to those mentioned above, and the arylsubstituents of which can be phenyl, tolyl, xylyl, naphthyl orbiphenylyl; and those substituted silyl groups which are bonded to thedonor atom or the acceptor atom via —CH₂—, for example (CH₃)₃SiCH₂—;C₆-C₁₂-aryloxy with the abovementioned aryl groups, C₁-C₈-perfluoroalkyland perfluorophenyl. Preferred substituents are: C₁-C₆-alkyl,C₅-C₆-cycloalkyl, phenyl, tolyl, C₁-C₆-alkoxy, C₆-C₁₂-aryloxy, vinyl,allyl, benzyl, perfluorophenyl, F, Cl, Br, di-(C₁-C₆-alkyl)-amino anddiphenylamino.

Donor groups are those in which the free electron pair is located on theN, P, As, Sb, Bi, O, S, Se, Te, F, Cl, Br and I; of these, N, P, O and Sare preferred. Examples of donor groups which may be mentioned are:(CH₃)₂N—, (C₂H₅)₂N—, (C₃H₇)₂N—, (C₄H₉)₂N—, (C₆H₅)₂N—, (CH₃)₂P—,(C₂H₅)₂P—, (C₃H₇)₂P—, (i-C₃H₇)₂P—, (C₄H₉)₂P—, (t-C₄H₉)₂P—,(cyclohexyl)₂P—, (C₆H₅)₂P—, CH₃O—, CH₃S—, C₆H₅S—, —C(C₆H₅)═O, —C(CH₃)═O,—OSi(CH₃)₃ and —OSi(CH₃)₂-t-butyl, in which N and P each carry a freeelectron pair and O and S each carry two free electron pairs, and wherein the last two examples mentioned, the double-bonded oxygen is bondedvia a spacer group, and systems, such as the pyrrolidone ring, where thering members other than N also act as spacers.

Acceptor groups are those in which an electron pair gap is present on B,Al, Ga, In or Tl, preferably B or Al; examples which may be mentionedare (CH₃)₂B—, (C₂H₅)₂B—, H₂B—, (C₆H₅)₂B—, (CH₃)(C₆H₅)₂B—, (vinyl)₂B—,(benzyl)₂B—, Cl₂B—, (CH₃O)₂B—, Cl₂Al—, (CH₃)₂Al—, (i-C₄H₉)₂Al—,(Cl)(C₂H₅)Al—, (CH₃)₂Ga—, (C₃H₇)₂Ga—, ((CH₃)₃Si—CH₂)₂Ga—, (vinyl)₂Ga—,(C₆H₅)₂Ga—, (CH₃)₂In—, ((CH₃)₃Si—CH₂)₂In—, (cyclopentadienyl)₂In—.

Those donor and acceptor groups which contain chiral centers or in which2 substituents form a ring with the D or A atom are furthermorepossible. Examples of these are, for example,

Preferred donor-acceptor bridges between CpI and CpII are, for example,the following:

One or both π systems πI and/or πII can be present as a heterocyclicring in the form of the above ring systems (a) to (r). D here ispreferably an element of main group 5 or 6 of the Periodic Table of theElements (Mendeleev); A here is preferably boron. Individual examples ofsuch hetero-π systems, in particular heterocyclic compounds, are:

Examples of heterocyclic radicals are: pyrrolyl, methylpyrrolyl,dimethylpyrrolyl, trimethylpyrrolyl, tetramethylpyrrolyl,t-butylpyrrolyl, di-t-butylpyrrolyl, indolyl, methylindolyl,dimethylindolyl, t-butylindolyl, di-t-butylindolyl,tetramethylphospholyl, tetraphenylphospholyl, triphenylphospholyl,trimethylphospholyl, phosphaindenyl, dibenzophospholyl(phosphafluorenyl) and dibenzopyrrolyl.

Preferred donor-acceptor bridges between πI and πII are, for example,the following: N→B, N→Al, P→B, P→Al, O→B, O→Al, Cl→B, Cl→Al, C═O→B andC═O→Al, where both atoms of these donor-acceptor bridges can be parts ofa hetero-π system or one atom (donor or acceptor) is part of a π systemand the other is a substituent of the second π system, or where bothatoms are substituents of their particular ring and one of the ringsadditionally contains a heteroatom.

According to the above described, the two ligand systems πI and πII canbe linked by one, two or three donor-acceptor bridges. This is possiblesince, according to the invention, formula (Ia) contains the D→A bridgedescribed, but the ligand systems πI and πII can carry further D and Aas substituents or hetero-π centers; the number of resulting additionalD→A bridges is zero, one or two. The number of D and A substituents onπI and πII respectively can be identical or different. The two ligandsystems πI and πII can additionally be bridged covalently. (Examples ofcovalent bridges are described further above as spacer groups.) However,compounds without a covalent bridge, in which πI and πII accordingly arelinked only via a donor-acceptor bridge, are preferred.

M represents a transition metal from sub-group 3, 4, 5 or 6 of thePeriodic Table of the Elements (Mendeleev), including the lanthanidesand actinides; examples which may be mentioned are: Sc, Y, La, Sm, Nd,Lu, Ti, Zr, Hf, Th, V, Nb, Ta and Cr. Ti, Zr and Hf are preferred.

In the formation of the metallocene structure or π complex structure, ineach case a positive charge of the transition metal M is compensated byin each case a cyclopentadienyl-containing carbanion. Positive chargeswhich still remain on the central atom M are satisfied by further,usually monovalent anions X, two identical or different anions of whichcan also be linked to one another (dianions x x), for examplemonovalently or divalently negative radicals from identical ordifferent, linear or branched, saturated or unsaturated hydrocarbons,amines, phosphines, thioalcohols, alcohols or phenols. Simple anionssuch as CR₃ ⁻, NR₂ ⁻, PR₂ ⁻, OR⁻, SR⁻ and the like can be connected bysaturated or unsaturated hydrocarbon or silane bridges, dianions beingformed and it being possible for the number of bridge atoms to be 0, 1,2, 3, 4, 5 or 6, 0 to 4 bridge atoms being preferred and 1 or 2 bridgeatoms particularly preferred. The bridge atoms can also carry furtherhydrocarbon substituents R in addition to H atoms. Examples of bridgesbetween the simple anions are, for example, —CH₂—, —CH₂—CH₂—, —(CH₂)₃—,CH═CH, —(CH═CH)₂—, —CH═CH—CH₂—, CH₂—CH═CH—CH₂—, —Si(CH₃)₂— and C(CH₃)₂—.Examples of X are: hydride, chloride, methyl, ethyl, phenyl, fluoride,bromide, iodide, the n-propyl radical, the i-propyl radical, the n-butylradical, the amyl radical, the i-amyl radical, the hexyl radical, thei-butyl radical, the heptyl radical, the octyl radical, the nonylradical, the decyl radical, the cetyl radical, methoxy, ethoxy, propoxy,butoxy, phenoxy, dimethylamino, diethylamino, methylethylamine,di-t-butylamino, diphenylamino, diphenylphosphino,dicyclohexylphosphino, dimethylphosphino, methylidene, ethylidene,propylidene and the ethylene glycol dianion. Examples of dianions are1,4-diphenyl-1,3-butadienediyl, 3-methyl-1,3-pentadienediyl,1,4-dibenzyl-1,3-butadienediyl, 2,4-hexadienediyl, 1,3-pentadienediyl,1,4-ditolyl-1,3-butadienediyl, 1 ,4-bis(trimethylsilyl-1,3-butadienediyland 1,3-butadienediyl. 1,4-Diphenyl-1,3-butadienediyl,1,3-pentadienediyl, 1,4-dibenzyl-1,3-butadienediyl, 2,4-hexanedienediyl,3-methyl-1,3-pentadienediyl, 1,4-ditolyl-1,3-butadienediyl and1,4-bis(trimethylsilyl)-1,3-butadienediyl are particularly preferred.Further examples of dianions are those with heteroatoms, for example ofthe structure

where the bridge has the meaning given. Weakly coordinating ornon-coordinating anions of the abovementioned type are moreoverparticularly preferred for charge compensation.

The activation by such voluminous anions is effective, for example, byreaction of the D/Aπ complex compounds, in particular the D/Ametallocenes, with tris-(pentafluorophenyl)-borane, triphenylborane,triphenylaluminum, trityl tetrakis-(pentafluorophenyl)-borate orN,N-dialkylphenylammonium tetrakis-(pentafluorophenyl)-borate or thecorresponding phosphonium or sulfonium salts of borates, or alkali metalor alkaline earth metal, thallium or silver salts of borates,carboranes, tosylates, triflates, perfluorocarboxylates, such astrifluoroacetate, or the corresponding acids. D/A metallocenes on whichthe anion equivalent X represents alkyl, allyl, aryl or benzyl groupsare preferably employed here. Such derivatives can also be prepared “insitu” by reacting D/A metallocenes with other anion equivalents, such asX=F, Cl, Br, OR and the like, beforehand with aluninum-alkyls,organomagnesium compounds, organolithium compounds or Grignard compoundsor zinc-, tin- or lead-alkyls. The reaction products obtainabletherefrom can be activated with abovementioned boranes or borateswithout prior isolation.

The index n assumes the value zero, one, two, three or four, preferablyzero, one or two, depending on the charge of M. The abovementionedsub-group metals can in fact assume valencies/charges of two to six,preferably two to four, inter alia depending on which of the sub-groupsthey belong to, in each case two of these valencies/charges beingcompensated by the carbanions of the metallocene compound. In the caseof La³⁺, the index n accordingly assumes the value one, and in the caseof Zr⁴⁺ it assumes the value two; in the case of Sm²⁺, n becomes zero.

To prepare the metallocene compounds of the formula (I), either in eachcase a compound of the above formulae (II) and (III) or in each case acompound of the above formulae (IV) and (V) or in each case a compoundof the above formulae (VI) and (VII) or in each case a compound of theabove formulae (VII) and (III) or in each case a compound of the aboveformulae (IV) and (IX) or in each case a compound of the above formulae(X) and (VII) can be reacted with one another, with elimination orsplitting off of alkali metal-X, alkaline earth metal-X₂, silyl-X,germyl-X, stannyl-X or HX compounds, in an aprotic solvent attemperatures from −78° C. to +120° C., preferably from −40° C. to +70°C., and in a molar ratio of (II):(III) or (IV):(V) or (VI):(VII) or(VIII):(III) or (IV):(IX) or (X):(VII) of 1:0.5-2, preferably 1:0.8-1.2,particularly preferably 1:1. In the cases of reaction of (VIII) with(III) or (IV) with (IX) or (X) with (VII), it is possible to dispensewith an aprotic solvent if (VIII), (IX) or (X) is liquid under thereaction conditions. Examples of those compounds eliminated or split offare: TlCl, LiCl, LiBr, LiF, LiI, NaCl, NaBr, KCl, KF, MgCl₂, MgBr₂,CaCl₂, CaF₂, trimethylchlorosilane, triethylchlorosilane,tri-(n-butyl)-chlorosilane, triphenylchlorosilane,trimethylchlorogermane, trimethylchlorostannane, dimethylamine,diethylamine, dibutylamine and other compounds which can be ascertainedby the expert from the abovementioned substitution pattern.

Compounds of the formula (II) and (IV) are thus carbanions which have acyclopentadienyl skeleton or a heterocyclic skeleton and contain 1 to 3donor groups, covalently bonded or incorporated as heterocyclic ringmembers and used for D/A bridge formation, and contain a cation as acounter-ion to the negative charge of the cyclopentadienyl skeleton.Compounds of the formula (VIII) are non-charged cyclic skeletons withlikewise 1 to 3 donor groups used for D/A bridge formation, but withleaving groups E(R¹R²R³) which can easily be split off, such as silyl,germyl or stannyl groups or hydrogen, instead of the ionic groups.

The second. component for formation of the metallocene compounds to beemployed according to the invention, that is to say the compound of theformula (III) or (V), is likewise a carbanion having a cyclopentadienylskeleton which is identical to the cyclopentadienyl skeleton of thecompound (II) or (IV) or different from this, but carries 1 to 3acceptor groups instead of the donor groups. In a corresponding manner,compounds of the formula (IX) are uncharged cyclopentadiene skeletonshaving 1 to 3 acceptor groups and likewise leaving groups F(R⁴R⁵R⁶)which can easily be split off.

In a completely analogous manner, compounds of the formulae (VI) or (X)are starting substances with a preformed D→A bond which arecarbanion-countercation compounds or uncharged cyclopentadienestructures with a possible 1 to 3 D→A bonds in total and give themetallocene compounds (I) by reaction with compounds of the formula(VII).

The two starting substances of the preparation process, that is to say(II) and (III) or (IV) and (V) or (VI) and (VII) or (VIII) and (III) or(IV) and (IX) or (X) and (VII) react spontaneously when broughttogether, with simultaneous formation of the donor-acceptor group —D→A—or complexing of the metal cation M with elimination of M′X orE(R¹R²R³)X or F(R⁴R⁵R⁶)X or HX. In the description of the donor-acceptorgroup, the substituents on D and A have been omitted for clarity.

M′ is one cation equivalent of an alkali metal or alkaline earth metal,such as Li, Na, K, ½Mg, ½C, ½Sr, ½Ba or thallium.

The compounds of the formula (XIIIa+b) are prepared analogously in theabovementioned manner.

Solvents for the preparation process are aprotic, polar or non-polarsolvents, such as aliphatic and aromatic hydrocarbons or aliphatic andaromatic halogeno-hydrocarbons. Other aprotic solvents such as are knownto the expert are also possible in principle, but, because of the easierworking up, those with boiling points which are too high are lesspreferred. Typical examples are: n-hexane, cyclohexane, pentane,heptane, petroleum ether, toluene, benzene, chlorobenzene, methylenechloride, diethyl ether, tetrahydrofuran and ethylene glycol dimethylether.

The starting substances of the formulae (II), (III), (IV) and (V) can beprepared by processes known from the literature or analogously to these.Thus, for example, trimethylsilyl-cyclopentadiene, which is available onthe market, can be reacted first with butyl-lithium and then withtrimethylsilyl chloride to give bis(trimethylsilyl)-cyclopentadieneanalogously to J. of Organometallic Chem. (1971), 29, 227. This productcan in turn be reacted with boron trichloride to givetrimethylsilyl-cyclopentadienyl-dichloroborane (analogously to J. ofOrgano-metallic Chem. (1979), 169, 327), which finally can be reactedwith titanium tetrachloride analogously to J. of Organometallic Chem.(1979), 169, 373 to give dichloroboryl-cyclopentadienyl-titaniumtrichloride. This compound mentioned last is already a prototype of thecompounds of the formula (III); the compound mentioned last canfurthermore be reacted selectively with trimethylaluminum, the twochlorine atoms bonded to the boron atom being replaced by methyl groups,a further compound of the formula (III) being demonstrated.Cyclopentadienyl-thallium, which is available on the market, can bereacted with chlorodiphenylphosphine and further with butyl-lithiumanalogously to the process descriptions in J. Am. Chem. Soc. (1983) 105,3882 and Organometallics (1982) 1, 1591, a prototype of compounds of theformula (II) being obtained. The formation ofdimethylstannyl-diphenylphosphine-indene by reaction of indene firstwith butyl-lithium, as already mentioned above, and then withchlorodiphenylphosphine may be mentioned as a further example; furtherreaction, first again with butyl-lithium and then withchloro-tributyltin, gives the compound mentioned, which, after furtherreaction with zirconium tetrachloride, givesdiphenylphosphino-indenyl-zirconium trichloride as a representative ofcompounds of the formula (IV). Such syntheses and preparation proceduresare familiar to the expert operating in the field of organometallic andorganoelemental chemistry and are published in numerous literaturereferences, of which only a few are given by way of example above.

The examples given further below show how such heterocyclic precursorsand catalysts according to the invention are accessible. Thus,pyrrolyl-lithium (formula II) can be prepared from pyrrole by reactionwith butyl-lithium, as described, for example, in J. Amer. Chem. Soc.(1982), 104, 2031. Trimethylstannyl-phosphol (formula VIII) is obtainedby reaction of 1-phenylphosphol with lithium, followed by aluminumtrichloride, phospholyllithium (formula II) being formed, which in turnfurther reacts with trimethylchlorostannane to givetrimethylstannyl-phosphol. cf.: J. Chem. Soc. Chem. Comm. (1988), 770.This compound can be reacted with titanium tetrachloride to givephospholyl-titanium trichloride (formula IV).

10¹ to 10¹² mol of comonomers are reacted per mole of π complexcompounds or metallocene compounds. The π complex compounds ormetallocene compounds can be employed together with cocatalysts. Theratio of the amounts between metallocene compound or π complex compoundand cocatalyst is 1 to 100,000 mol of cocatalyst per mole of metalloceneor π complex compound. Cocatalysts are, for example, aluminoxanecompounds. These are understood as meaning those of the formula

in which

R represents C₁-C₂₀-alkyl, C₆-C₁₂-aryl or benzyl and

n denotes a number from 2 to 50, preferably 10 to 35.

It is also possible to employ a mixture of various aluminoxanes or amixture of precursors thereof (aluminum-alkyls) in combination withwater (in gaseous, liquid, solid or bonded form, for example as water ofcrystallization). The water can also be fed in as (residual) moisture ofthe polymerization medium, of the monomer or of a support, such assilica gel.

The bonds projecting from the square brackets of formula (XI) contain Rgroups or AlR₂ groups as end groups of the oligomeric aluminoxane. Suchaluminoxanes are as a rule present as a mixture of two or more thereofhaving different chain lengths. Fine analysis has also shownaluminoxanes with a cyclic or cage-like structure. Aluminoxanes arecompounds which are available on the market. In the specific case ofR=CH₃, methylaluminoxanes (MAO) are referred to.

Further cocatalysts are aluminum-alkyls, lithium-alkyls or organo-Mgcompounds, such as Grignard compounds, or partly hydrolyzed organoboroncompounds. Preferred cocatalysts are aluminoxanes.

The activation with the cocatalyst or the introduction of the voluminousnon- or weakly coordinating anions can be carried out in an autoclave orin a separate reaction vessel (preforming). The activation can becarried out in the presence or absence of the monomer(s) to bepolymerized. The activation can be carried out in an aliphatic oraromatic or halogenated solvent or suspending agent.

The π complex compounds or the metallocene compounds and thealuminoxanes or the boron-containing activators can be employed both assuch in homogeneous form and individually or together in heterogeneousform on supports. The support material here can be inorganic or organicin nature, such as silica gel, Al₂O₃, MgCl₂, NaCl, cellulosederivatives, starch and polymers. It is possible here both to applyfirst the π complex compound or the metallocene compound and to applyfirst the aluminoxane or the boron-containing activators to the support,and then to add the other respective component. However, it is equallypossible also to activate the π complex compound or metallocene compoundin homogeneous or heterogeneous form with the aluminoxane or a suitableboron compound and then to apply the activated metallocene compound tothe support, which is laden with aluminoxane where appropriate.

Support materials are preferably pretreated by heat and/or withchemicals in order to adjust the water content or the OH groupconcentration to a defined value or to keep it as low as possible. Achemical pretreatment can comprise, for example, reaction of the supportwith aluminum-alkyl. Inorganic supports are usually heated at 100° C. to1000° C. for 1 to 100 hours before use. The surface area of suchinorganic supports, in particular of silica (SiO₂), is between 10 and1000 m²/g, preferably between 100 and 800 m²/g. The particle diameter isbetween 0.1 and 500 micrometers (μ), preferably between 10 and 200 μ.

Olefins, diolefins, halogenated diolefins, (meth)acrylates and vinylesters which are to be reacted by (co)polymerization are, for example,ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, oct-1-ene,3-methyl-but-1-ene, 4-methyl-pent-1-ene, 4-methyl-hex-1-ene,1,3-butadiene, isoprene, 1,4-hexadiene, 1,5-hexadiene and 1,6-octadiene,chloroprene, vinyl acetate, vinyl propionate and others known to theexpert. Such olefins and diolefins can furthermore be substituted, forexample by phenyl, substituted phenyl, halogen, the esterified carboxylgroup or the acid anhydride group; compounds of this type are, forexample, styrene, methylstyrene, chlorostyrene, fluorostyrene, indene,4-vinyl-biphenyl, vinyl-fluorene, vinyl-anthracene, methyl methacrylate,ethyl acrylate, vinylsilane, trimethylallylsilane, vinyl chloride,vinylidene chloride, tetrafluoroethylene, vinylcarbazole,vinyl-pyrrolidone, vinyl ethers and vinyl esters. Preferred monomersare: ethylene, propylene, butene, hexene, octene, 1,4-hexadiene,1,6-octadiene, methyl methacrylate and acetylene.

In addition to the dienes mentioned, the following may further bementioned as open-chain, mono- and polycyclic dienes:5-methyl-1,4-hexadiene and 3,7-dimethyl-1,6-octadiene; cyclopentadiene,1,4-hexadiene, 1,5-cyclooctadiene; tetrahydroindene,methyl-tetrahydroindene, dicyclopentadiene,bicyclo-(2,2,1)-hepta-2,5-diene and norbornenes with substituents, suchas alkenyl, alkylidene, cycloalkenyl and cycloalkylidene, thus forexample 5-methylene-2-norbomene (B), 5-ethylidene-2-norbomene,5-isopropylidene-2-norbornene; and allylcyclohexene andvinyl-cyclohexene.

Further preferred monomers, in addition to those mentioned above, are:dicyclopentadiene, 1,4-hexadiene, 5-methyl-2-norbornene,5-ethylidene-2-norbornene and 5-vinyl-2-norbornene. Mixtures of severalof these can of course be employed.

The process according to the invention is carried out in the bulk,solution, slurry or gas phase, depending on whether a soluble or aninsoluble catalyst of the type described above is employed. The solutionphase or the slurry phase can be formed from the comonomers alone, i.e.without the use of an additional solvent. In the case where a solvent isalso used, possible solvents for this are inert solvents, for examplealiphatic or cycloaliphatic hydrocarbons, benzine or diesel oilfractions (if appropriate after a hydrogenation), toluene,chlorobenzene, o-dichlorobenzene or chloronaphthalene. In the case ofsolvents of low boiling point, it can be ensured that the liquid phaseis maintained by applying an adequate reaction pressure; suchrelationships are known to the expert. According to the invention, thereaction is carried out discontinuously or continuously or in thesemi-batch process.

The abovementioned temperatures and pressures are used. Temperatures inthe lower range, for example 0 to 150° C., are preferred for the bulk,solution and slurry procedures, and temperatures in the range from about20 to 100° C. are preferred for the gas phase. For economic reasons, thepressures often do not exceed the value of 30 bar, preferably 20 bar.According to the invention, the reaction is carried out in one or morereactors or reaction zones, for example in a reactor cascade; in thecase of several reactors, different polymerization conditions can beestablished.

Thermoplastic elastomers (TPE) are characterized by successive blocks(sequences) which are alternately of either high order and thereforehave a high crystallinity or of low order and therefore have a low orcomplete lack of crystallinity. The crystalline blocks melt on heatingand render the substance thermoplastically processible, and theunordered amorphous blocks are elastic buffers between the crystalline,ordered blocks and impart to the substance elastomeric propertiesoverall. These include, in particular, good extensibility, flexibilityand a low proportion of residual deformation coupled with goodmechanical properties, in particular a high impact strength. Such TPEsare suitable, for example, for cable sheathing, hoses, in particularalso in the medical sector, shrink films, window seals and the like.

During the preparation of thermoplastic elastomers, alternatingpolymerization conditions must accordingly be established, under whichordered or unordered blocks are formed.

In the case of monomers having 3 or more C atoms, with the same chemicalcomposition, that is to say the use of only one monomer, such structuresare possible. This may be shown in the form of a formula as follows,using the example of thermoplastic-elastomeric propylene (e-PP):

i=isotactic, s=syndiotactic, a=atactic, n=number of recurring units.

In both cases, highly ordered isotactic or syndiotactic and thereforecrystalline blocks alternate with unordered atactic and thereforeelastic blocks. e-PP is an important representative of thermoplasticelastomers. Such block structures also result analogously from 1-butene,1-hexene, styrene, 3-methyl-1-pentene, 4-methyl-1-pentene and othermonomers known to the expert.

However, the elastic block can also be formed by elastomer structures ofwhich the monomers or comonomers differ chemically from the monomer ofthe crystalline block, so that overall a copolymer of at least 2different comonomers is formed. Examples of this type are:

(PE—EPM)_(n)

(PE—EBM)_(n)

(PE—EHM)_(n)

(PE—EOM)_(n)

where E=ethylene, P=propylene, B=butene, H=hexene, O=octene.

Further examples are:

(PE—a-PP)_(n)

(i-PP—EPM (and —EBM or —EHM or —EOM))_(n)

(s-PP—EPM (and —EBM or —EHM or —EOM))_(n)

The crystalline phase can also be built up on the basis of highly tactic(iso- or syndio-) structures of polybutene, polyhexene or polyoctene;conversely, the atactic structures of these polymers form suitableamorphous phases.

By incorporation of dienes, for example, the following are obtained:

(PE—EPDM)_(n)

(i-PP—EPDM)_(n)

(s-PP—EPDM)_(n)

In all the examples mentioned, the block mentioned first in the terms inparentheses is the highly crystalline content and the block mentionedthereafter is the non-crystalline, randomly built-up content, forexample PE is a predominantly or exclusively ethylene-containing block(including LLDPE), while, for example, a-PP is a non-crystalline,atactic and predominantly or exclusively propene-containing block.

The π complex compounds, in particular the metallocene compounds, to beemployed according to the invention allow, due to the donor-acceptorbridge, a defined opening of the two cyclopentadienyl skeletons like abeak, a controlled molecular weight distribution and uniformincorporation of (co)monomers being ensured, in addition to a highactivity. As a result of a defined beak-like opening, there is alsospace for voluminous (co)monomers. The high uniformity in molecularweight distribution is furthermore optionally results from the uniformand defined site of the polymerization which takes place by insertion(single site catalyst) and can be established by the choice ofpolymerization temperature.

The molecular weight distribution can be modified (broadened) in acontrolled manner by employing several D/A catalysts simultaneously, inorder to establish a certain profile of properties of the material.Accordingly, it is also possible to employ one or more D/A catalysts incombination with other metallocenes which have no D/A bridge.

The simultaneous use of at least two metallocene catalysts, at least oneof which is a D/A metallocene and which have differentstereoselectivities, for example one for a-PP and another for i-PP, canbe utilized effectively for developing an optimum TPE by balancedparticipation of the amorphous and crystalline phases.

The D/A structure can have the effect of extra-stabilizing the catalystsup to high temperatures, so that the catalysts can also be employed inthe high temperature range from 80 to 250° C., preferably 80 to 180° C.The possible thermal dissociation of the donor-acceptor bond isreversible and, as a result of this self-organization process andself-repair mechanism, leads to particularly high-quality catalystproperties.

It has furthermore been found that metallocene compounds to be employedaccording to the invention show different copolymerization properties,depending on the temperature. This phenomenon has not yet beeninvestigated completely, but could coincide with the observation thatcoordinate bonds which are overlapped by an ionic bond, such as thedonor-acceptor bonds in the metallocene compounds according to theinvention, show an increasing reversibility at a higher temperature. Ithas thus been observed, for example in the case of ethylene-propylenecopolymerization, that if the same amount of the two comonomers isavailable, a highly propylene-containing copolymer is formed at a lowcopolymerization temperature, while as the polymerization temperatureincreases, the propylene content decreases, until finally predominantlyethylene-containing polymers are formed at a high temperature. Thereversible dissociation and association of the D/A structure and therotation of the π skeletons against one another which become possible asa result can be shown schematically as follows:

By changing between a bridged and non-bridged catalyst structure,catalysts which are suitable for generating varyingstereospecific/aspecific ligand arrangements or else a varying substrateselectivity in a defined manner using only one catalyst under varyingconditions are available for the first time.

Another valuable property of the D/A-π complex compounds, for exampleD/A metallocene compounds, according to the invention is the possibilityof self-activation and therefore of dispensing with expensivecocatalysts, in particular in the case of dianionic xx derivatives.

In this case, the acceptor atom A in the open form of the D/A-π complexcompounds, for example D/A metallocene compound, bonds an X ligand, forexample one side of a dianion, to form a zwitterionic metallocenestructure, and thus generates a positive charge in the transition metal,while the acceptor atom A assumes a negative charge. Such aself-activation can be intramolecular or intermolecular. This may beillustrated by the example of the preferred linkage of two X ligands toa chelate ligand, that is to say of the butadienediyl derivative:

The bonding site between the transition metal M and H or substituted orunsubstituted C, in the formula example substituted C of thebutadienediyl dianion shown, is then the site for the olefin insertionfor the polymerization.

The temperature-dependent dynamic properties of the π complex compoundsand metallocene compounds according to the invention at varioustemperatures accordingly allows the preparation, at varioustemperatures, of different stereo-block copolymers, for example those ofthe type of isotactic and atactic polypropylene (i-PP-aPP)_(n), whichcan be of different composition (a) with respect to the relative amountsof isotactic polypropylene (i-PP) and atactic polypropylene (a-PP), and(b) with respect to the block or sequence lengths.

The π complex compounds or metallocene compounds to be employedaccording to the invention are correspondingly suitable for thepreparation of thermoplastic elastomers. According to the abovedescription, these are distinguished by block structures which havealternately amorphous and crystalline properties. The crystallineregions can be achieved here by intramolecular and/or intermolecularstates of order. Such crystalline states are reversible physicalcrosslinking sites for the elastomer.

EXAMPLES

All the reactions were carried out under strictly anaerobic conditionsusing Schlenk techniques or the high vacuum technique. The solvents usedwere dry and saturated with argon. Chemical shifts δ are stated in ppm,relative to the particular standard: ¹H(tetramethylsilane),¹³C(tetramethylsilane), ³¹P(85% strength H₃PO₄), ¹¹B(boron trifluorideetherate-18.1 ppm). Negative signs denote a shift to a higher field.

Example 1 (Bis-(trimethylsilyl)-cyclopentadiene, compound 1)

14.7 g (0.106 mol) of trimethylsilyl-cyclopentadiene (obtained fromFluka) and 150 ml of tetrahydrofuran (THF) were introduced into areaction flask and cooled to 0° C. 47.4 ml of a solution ofbutyl-lithium in n-hexane (2.3 molar; total amount 0.109 mol) were addeddropwise to this in the course of 20 minutes. When the addition wascomplete, the yellow solution was stirred for a further hour;thereafter, the cooling bath was removed. The solution was stirred for afurther hour at room temperature and then cooled to −20° C. 14.8 ml(0.117 mol) of trimethylsilyl chloride were then added dropwise in thecourse of 10 minutes and the reaction mixture was stirred at −10° C. fortwo hours. Thereafter, the cooling bath was removed and the reactionsolution was warmed to room temperature and subsequently stirred for afurther hour. The reaction mixture was filtered through Celite; thefilter was washed with hexane and the hexane was removed from thecombined filtrates in vacuo. On distillation at 26° C. under 0.4 mbar,the crude product gave 19 g of pure product of the compound 1 (85% ofthe theoretical yield). The boiling point and NMR data correspond to theliterature data (J. Organometallic Chem. 29 (1971), 227; ibid. 30(1971), C 57; J. Am. Chem. Soc. 102, (1980), 4429; J. Gen. Chem. USSR,English translation 43 (1973), 1970; J. Chem. Soc., Dalton Trans. 1980,1156)

¹H-NMR (400 MHz, C₆D₆): δ=6.74 (m, 2H), 6.43 (m, 2H), −0.04 (s, 18H).

Example 2 (Trimethylsilyl-cyclopentadienyl-dichloroborane, compound 2)

16 g (0.076 mol) of the compound 1 were introduced into a round-bottomedflask equipped with a dry ice cooling bath. 8.9 g (0.076 mol) of BCl₃were condensed at −78° C. in a Schlenk tube and then added dropwise tothe round-bottomed flask over a period of 5 minutes. The reactionmixture was warmed slowly to room temperature in the course of 1 hourand then kept at 55 to 60° C. for a further 2 hours. All the volatilecompounds were removed in vacuo (3 mm Hg=4 mbar). Subsequentdistillation at 39° C. under 0.012 mbar gave 14.1 g of the compound 2(85% of the theoretical yield). The ¹H-NMR agreed with the literaturedata and showed that a number of isomers had been prepared (cf. J.Organometallic Chem. 169 (1979), 327). ¹¹B-NMR (64.2 MHz, C₆D₆):δ=+31.5.

Example 3 (Dichloroboranyl-cyclopentadienyl-titanium trichloride,compound 3)

11.4 g (0.052 mol) of the compound 2 and 100 ml of methylene chloride(CH₂Cl₂) were introduced into a 250 ml Schlenk tube. This solution wascooled to −78° C., and 9.8 g (5.6 ml, 0.052 mol) of titaniumtetrachloride were added dropwise in the course of 10 minutes. Theresulting red solution was warmed slowly to room temperature and stirredfor a further 3 hours. The solvent was removed in vacuo and a dirtyyellow product was obtained. 200 ml of hexane were added to the crudesolid and the resulting yellow solution was filtered and cooledovernight in a refrigerator, 12.3 g (79% of the theoretical yield) ofyellow crystals of the compound 3 being obtained. It should be pointedout that in J. Organometallic Chem. 169 (1979), 373, 62% of thetheoretical yield was obtained, the reaction being carried out in ahydrocarbon solvent, such as petroleum ether or methylcyclohexane.

¹H-NMR (400 MHz, CD₂Cl₂): δ=7.53 (t, J=2.6 Hz, 2 H), 7.22 (t, J=2.6 Hz2H). ¹¹B-NMR (64.2 MHz, CD₂Cl₂): δ=+33.

Example 4 (Dimethylboranyl-cyclopentadienyl-titanium trichloride,compound 4)

2.37 g (0.0079 mol) of the compound 3 were dissolved in 100 ml of hexanein a round-bottomed flask. This solution was cooled to 0° C. and 4 ml ofa 2 molar solution of aluminum-trimethyl in toluene (0.008 mol) wereadded dropwise. When the addition was complete, the cooling bath wasremoved and all the volatile fractions were removed in vacuo. The yellowsolid which remained was now dissolved in pentane, solid fractions werefiltered off and the clear filtrate was cooled to −78° C., 1.5 g (74% ofthe theoretical yield) of compound 4 being obtained. It should be notedthat in J. Organometallic Chem. 169 (1979), 373 a yield of 87% of thetheoretical yields is stated, tetramethyltin being used as thealkylating agent; however, it was not possible to obtain the compound 4in a form free from the trimethyltin chloride formed.

¹H-NMR (400 MHz, CD₂Cl₂): δ=7.48 (t, J=2.5 Hz, 2H), 7.23 (t, J=2.5 Hz,2H), 1.17 (s, 6H). ¹¹B-NMR (64.2 MHz, CD₂Cl₂): δ=+56.

Example 5 (Diphenylphosphine-cyclopentadienyl)-lithium, compound 6)

50 g (0.186 mol) of cyclopentadienyl-thallium (obtained from Fluka) wereintroduced together with 300 ml of diethyl ether into a 500 ml flask.The suspension was cooled to 0° C. and 34.2 ml (0.186 mol) ofdiphenylchlorophosphine were added dropwise in the course of 10 minutes.The suspension was then warmed to room temperature and stirred for onehour, and finally filtered through a frit. The solvent was then strippedoff in vacuo and left behind 39.5 g (85% of the theoretical yield) ofthe intermediate product diphenylphosphinocyclopentadiene, compound 5. Acontent of 18.6 g (0.074 mol) of the compound 5 was then diluted withtoluene and cooled to 0° C. 33.2 ml of a 2.24 molar solution ofbutyl-lithium in hexane (0.074 mol) were added to this solution in thecourse of minutes. After warming to room temperature and after stirringfor 2 hours, the yellow solution gave a precipitate, which was filteredoff and washed with toluene and then with hexane. After drying in vacuo,13.2 g of the compound 6 (70% of the theoretical yield) were obtained asa brownish powder (cf. J. Am. Chem. Soc. 105 (1983), 3882;Organometallics 1 (1982), 1591).

¹H-NMR (400 MHz, d₈THF): δ=7.3 (m, 4H), 7.15 (m, 6H), 5.96 (m, 2H), 5.92(m, 2H), ³¹P-NMR (161.9 MHz, d₈THF): δ=−20.

Example 6 ((C₆H₅)₂P→B(CH₃)₂-bridged bis-(cyclopentadienyl)-titaniumdichloride, compound 7)

0.36 g (0.00139 mol) of the compound 6 and 20 ml of toluene wereintroduced into a round-bottomed flask. The solution formed was cooledto −20° C. and a solution of 0.36 g (0.00139 mol) of the compound 4 in20 ml of toluene was added dropwise in the course of 20 minutes. Whenthe dropwise addition had ended, the solution was heated to roomtemperature in the course of 2 hours and stirred at this temperature foran additional hour. Insoluble material was removed over a frit and thesolvent was distilled off in vacuo. The red oily solid was then washedwith hexane, which was decanted off, and the solid was dried again invacuo. 0.28 g (42% of the theoretical yield) of the compound π wasobtained as a red powder by this procedure.

¹H-NMR (300 MHz, CD₂Cl₂): δ=7.6-7.3 (br, m, 10H), 6.92 (m, 2H), 6.77 (m,4H), 6.60 (m, 2H), 0.29 (d, J_(PH)=19 Hz, 61); 31P-NMR (161.9 MHz,CD₂Cl₂): δ=17.1 (br); ¹¹B-NMR (64.2 MHz, CD₂Cl₂): δ=−29 (br).

Example 7 (Tributylstannyl-diphenylphosphino-indene, compound 8)

10 g (0.086 mol) of indene were introduced into a round-bottomed flask,diluted with 200 ml of diethyl ether and cooled to −20° C. 36 ml of a2.36 molar solution of butyl-lithium (0.085 mol) in n-hexane were addedto this solution, the solution immediately assuming a yellow color. Thecooling bath was removed and the reaction mixture was allowed to warm toroom temperature and was stirred for a further hour. Thereafter, thereaction mixture was cooled again to 0° C. and 19 g (15.9 ml, 0.086 mol)of diphenylchlorophosphine were added, a precipitate being formed. Thecooling bath was removed again and the solution was allowed to warm toroom temperature while being subsequently stirred for a further hour.The solution was then cooled again to −20° C. and 36 ml (0.085 mol) ofbutyl-lithium in n-hexane were added dropwise. When the addition hadended, the cooling bath was removed again and the temperature rose toroom temperature; the solution was subsequently stirred for a further1.5 hours. The suspension was then cooled again to 0° C. and 28 g (0.086mol) of tributyltin chloride were added dropwise. The resultingsuspension was warmed to room temperature and stirred for a further 1.5hours and subsequently filtered through a frit, and the solvent wasremoved in vacuo. 46.9 g of the compound 8 (92% of the theoreticalyield) remained as a heavy yellow oil.

¹H-NMR (400 MHz, CDCl₃): δ=7.5-7.3 (m, 6H), 7.28 (br s, 6H), 7.14(pseudo-d t, 7.3 Hz/1.0 Hz, 1H), 7.08 (t, J=7.3 Hz, 1H), 6.5 (br m, 1H),4.24 (br s, 1H), 1.4-1.25 (m, 6H), 1.25-1.15 (m, 6H), 0.82 (t, J=7.2 Hz,9H), 0.53 (t, J=8 Hz, 6H), ³¹P-NMR (161.9 MHz, CDCl₃): δ=−20.6.

Example 8 (Diphenylphosphino-indenyl-zirconium trichloride, compound 9)

A solution of 37 g (0.0628 mol) of the compound 8 in 300 ml of toluenewas added to a suspension of 14.6 g of ZrCl₄ (99.9% pure, 0.0628 mol,obtained from Aldrich) in 100 ml of toluene at room temperature in thecourse of 3 hours. The solution immediately became red and slowlychanged into orange and finally into yellow. After subsequently stirringfor 4 hours, the yellow precipitate was filtered off and washed withtoluene and then with hexane. The solid was dried in vacuo and gave 15.3g (50% of the theoretical yield) of the compound 9 as a free-flowingyellow powder. The yield could easily be increased to more than 70% bycarrying out the reaction at a lower temperature, for example 30 minutesat −30° C. and 5 hours at 0° C. The product could be purified further bywashing out residual tin compound using pentane in a Soxhlet extractor(extraction time: 8 hours).

Example 9 ((C₆H₅)₂P-BCl₂-bridged indenyl-cyclopentadienylzirconiumdichloride, compound 10)

4.43 g (0.0089 mol) of the purified compound 9 and 100 ml of toluenewere introduced into a Schlenk tube. 1.95 g (0.0089 mol) of the compound2 were added to this suspension. The yellow suspension was stirred atroom temperature for 6 hours; during this period, a pale whiteprecipitate formed. This precipitate (4.1 g, 75% of the theoreticalyield) was isolated by filtration and found to be essentially purematerial.

¹H-NMR (500 MHz, CD₂Cl₂): δ=7.86 (pseudo ddd, J=8.5/2.5/1 Hz, 1H),7.75-7.55 (m, 10H), 7.35 (pseudo ddd, J=8.5/6.9/0.9 Hz, 1H), 7.32 (br t,J=3.1 Hz, 1H), 7.22 (pseudo ddd, J=8.8/6.8/1.1 Hz, 1H), 7.06 (pseudoddd, J=3.4/3.4/0.8 Hz, 1H), 6.92 (m, 1H), 6.72 (m, 1H), 6.70 (br m, 1H),6.61 (pseudo q, J=2.3 Hz, 1H), 6.53 (br d, 8.7 Hz, 1H); ³¹P-NMR (161.9MHz CD₂Cl₂): δ=6.2 (br, m); ¹¹B-NMR (64.2 MHz, CD₂Cl₂): δ=−18 (br).

Example 10 ((C₆H₅)₂P-B (CH₃)₂-bridged indenyl-cyclopentadienylzirconiumdichloride, compound 11)

50 ml of toluene were added to 1.5 g (0.00247 mol) of compound 10 fromExample 9. The suspension was cooled to 0° C. and 1.2 ml of a 2 molarsolution of trimethylaluminum in hexane (0.0024 mol) were added dropwiseto this in the course of 5 minutes. When the addition was complete, thecooling bath was removed and the solution was allowed to warm up to roomtemperature and was further stirred for 2 hours. The remainingprecipitate was filtered off and the solvent was stripped off from thefiltrate in vacuo, 0.37 g (26% of the theoretical yield) of the compound11 remaining as a brownish solid.

³¹P-NMR (161.9 MHz, CD₂Cl₂): δ=14.6; ¹¹B-NMR (64.2 MHz, CD₂Cl₂): δ=−28

Example 11 (Trimethylsilyl-indene, compound 12)

25 ml of indene (0.213 mol distilled over CaH₂ in vacuo) were introducedinto a round-bottomed flask which contained 100 ml of THF and was cooledto 0° C. 94 ml of a 2.3 molar solution of butyl-lithium in hexane (0.216mol) were added in the course of 20 minutes. When the addition wascomplete, the mixture was stirred for 20 minutes and then warmed to roomtemperature and stirred for a further 30 minutes. After cooling to −20°C., 27.5 ml (0.216 mol) of trimethylchlorosilane were added dropwise, aslightly cloudy orange-colored solution being formed. After stirring at−10° C. for I hour and at 0° C. for 1.5 hours, the solution was warmedto room temperature and the solvent was removed in vacuo. Afterdissolving again in hexane, LiCl was filtered off and the hexane wasremoved in vacuo. Distillation of the product (0.045 mbar, 58 to 60° C.)gave 26.6 g (66% of the theoretical yield) of 12.

¹H-NMR (400 MHz, CDCl₃): δ=7.49 (t, J=7.6 Hz, 1H), 7.28 (ddd,J=7.3/7.2/1 Hz, 1 H), 7.21 (ddd, J=7.3/7.3/1.1 Hz, 1 H), 6.96 (dd,J=5.6/1.2 Hz, 1 H), 6.69 (dd, J=5.3/1.8 Hz, 1 H), 3.56 (s, 1 H), 0.0 (s,9 H).

Example 12 (Bis-(trimethylsilyl)-indene (compound 13)

25.4 g (0.135 mol) of the compound 12 were introduced into around-bottomed flask which contained 100 ml of THF and was cooled to 0°C. 59 ml of a 2.3 molar solution of butyl-lithium in hexane (0.136 mol)were added in the course of 20 minutes. When the addition was complete,the mixture was stirred for 20 minutes and then warmed to roomtemperature. After stirring for 30 minutes, it was cooled to −20° C. and17.3 ml of trimethylchlorosilane (0.136 mol) were added dropwise, aslightly cloudy orange-colored solution being formed. The solution wasstirred at 0° C. for 1 hour and at room temperature for 1 hour and thesolvent was then removed in vacuo. After redissolving in hexane, LiClwas filtered off and the hexane was removed in vacuo. 32 g (90% of thetheoretical yield) of 13 were obtained as an oil. cf. J. Organometal.Chem. 23 (1970), 407; hexane there instead of THF.

¹H-NMR (400 MHz, CDCl₃): δ=7.62 (d, J=7.6 Hz, 1 H), 7.52 (d, J=7.5 Hz, 1H), 7.23 (ddd, J=7.35/7.3/0.9 Hz, 1 H), 6.9 (d, J=1.7 Hz, 1 H), 3.67 (d,J=1.6 Hz, 1 H), 0.38 (s, 9 H), 0.0 (s, 9 H).

Example 13 (Trimethylsilyl-dichloroboranyl-indene, compound 14)

In a manner similar to the preparation of compound 2, 12.3 g (0.047 mol)of compound 13 were introduced into a round-bottomed flask which wascooled to −30° C. and had a reflux condenser cooled with dry ice. 5.6 g(0.046 mol) of BCl₃ were added to this. When the addition was complete,the cooling bath was removed and the reaction mixture warmed to roomtemperature and was stirred for 3 hours. The temperature was then raisedto 55° C. for 6 hours. After cooling and removal of the volatilecontents in vacuo, the crude product was obtained. Distillation under ahigh vacuum gave the purified product, the main isomer of which wasidentified as follows:

¹H-NMR (200 MHz, CDCl₃): δ=8.3 (d, J=π Hz, 1 H), 8.1 (d, J=1.8 Hz, 1 H),7.5 (dd, J=7.0/1.2 Hz, 1 H), 7.4 (m, 3 H), 4.0 (d, J=1.8 Hz, 1 H), 0.1(s, 9 H); ¹¹B-NMR (64.2 MHz, CD₂Cl₂): δ=38 (br).

Example 14 ((C₆H₅)₂P-BCl₂-bridged bis-(indenyl)-zirconium dichloride,compound 15)

4.5 g of the compound 14 (0.017 mol) were added to a suspension of 8.3 gof compound 9 (0.017 mol) in 200 ml of toluene; the mixture was heatedto 50° C. and stirred for 5 hours. After cooling and filtration, 200 mlof hexane were added, after which a precipitate precipitated out of theclear yellow solution and was filtered off and dried in vacuo. Theproduct was identified as the meso-isomer of 15 according to its X-rayanalysis. The P→B bond length of the bridge was determined as 2.01 Å. Asecond precipitate, which was determined as the racemic isomer of 15,was obtained by concentration of the toluene/hexane solution to about 10ml and further addition of 200 ml of hexane.

Example 15 (N,N-Dimethyl-O-(methylsulfonyl)-hydroxylamine, compound 16)

(CH₃)₂NOSO₂CH₃  16

9.0 g of N,N-dimethyl-O-hydroxylamine hydrochloride (0.092 mol) weresuspended in 70 ml of CH₂Cl₂ which contained 20 g of triethylamine (0.2mol), and the suspension was cooled to −10° C. 9.5 g of methylsulfonylchloride (0.083 mol), dissolved in 70 ml of CH₂Cl₂, were slowly addeddropwise to the cooled suspension. When the addition was complete, themixture was subsequently stirred for 1 hour. Thereafter, ice-water wasadded to the reaction mixture and the organic phase was separated off.The water which remained was washed with ether. The wash ether and theCH₂Cl₂ fraction were combined and dried over Na₂SO₄ and the solventswere removed in vacuo at −10° C. 5.9 g (46% of the theoretical yield) ofcompound 16 remained as an oil, which was stored at −20° C. cf. Angew.Chem. Int. Ed. Engl. 17 (1978), 687.

¹H-NMR (400 MHz, CDCl₃): δ=3.03 (s, 3H), 2.84 (s, 6H).

Example 16 (N,N-Dimethylamino-cyclopentadienyl-lithium, compound 17)

A solution of 3 g of cyclopentadienyl-lithium (0.042 mol) in 30 ml ofTHE was slowly added to a solution of 5.9 g of the compound 16 (0.042mol) in 20 ml of THF at −30° C. The mixture was then warmed to −20° C.and stirred for 30 minutes. Hexane was then added and the solution wasfiltered. Thereafter, 1.8 ml of a 2.3 molar solution of butyl-lithium(0.042 mol) in hexane were added at −20° C., whereupon a precipitateformed. The precipitate was filtered off and washed twice with 20 ml ofhexane each time. After drying in vacuo, 2.0 g (40% of the theoreticalyield) of the compound 17 were obtained as a white powder. cf. Angew.Chem. Int. Ed. En. 19 (1980), 1010.

¹H-NMR (400 MHz, THF): δ=5.34 (br d, J=2.2 Hz, 2H), 5.15 (br d, J=2.2Hz, 2H), 2.56 (s, 6H).

Example 17 ((CH₃)₂N-B(CH₃)₂-bridged bis-(cyclopentadienyl)-titaniumdichloride, compound 18)

A solution of 0.18 g of the compound 4 (0.7 mmol) in 10 ml of toluenewas added to a suspension of 0.081 g of the compound 17 (0.7 mmol) in 10ml of toluene at −20° C. in the course of 10 minutes, a deep redsolution being formed. After warming at room temperature for 2 hours,the solution was filtered and the solvent was removed in vacuo. Afterthe red powder formed had been redissolved in 10 ml of warm toluene andinsoluble material had been filtered off, the solution was storedovernight in a refrigerator, 0.1 g (43% of the theoretical yield) beingformed as red needles.

¹H-NMR (400 MHz, CD₂Cl₂): δ=6.85 (t, J=2.3 Hz, 2H), 6.15 (t, J=2.3 Hz,2H), 6.1 (t, J=2.8 Hz, 2H), 5.57 (t, J=2.8 Hz, 2H), 1.98 (s, 6H), 0.35(s, 6H ); ¹¹B-NMR (64.2 MHz, CD₂Cl₂): δ=2.8 (br).

Example 18 (Tributylstannyl-diisopropylphosphine-indene, compound 19)

100 ml of ether were introduced into a round-bottomed flask whichcontained 3.8 g (0.033 mol) of indene; the mixture was cooled to −20° C.14.4 ml of a 2.3 molar solution of butyl-lithium in hexane (0.033 mol)were added to this solution in the course of 5 minutes, a yellowsolution being formed. After removal of the cooling bath, the solutionwas warmed to room temperature and subsequently stirred for 1.5 hours.Thereafter, the reaction mixture was cooled to 0° C. and 5.0 g ofchlorodiisopropylphosphine (0.033 mol) were added, whereupon aprecipitate formed. After removal of the cooling bath, the solution waswarmed to room temperature and stirred for 1 hour. Thereafter, thesolution was cooled to −20° C. and 14.4 ml of a 2.3 molar solution ofbutyl-lithium in hexane (0.033 mol) were added dropwise. When theaddition was complete, the cooling bath was removed and the solution waswarmed slowly to room temperature and subsequently stirred for 1.5hours. After the suspension had been cooled to 0° C., 10.1 g ofchlorotributyltin (0.031 mol) were added dropwise. The suspension formedwas warmed to room temperature and stirred for 1.5 hours. The ether wasremoved in vacuo and the crude product was dissolved again in hexane,the solution was filtered and the filtrate was dried in vacuo, 16.6 g ofthe compound 19 (yield: 97%) remaining as a heavy yellow oil. Twoisomers were obtained in a ratio of 1.5:1. The main isomer wasidentified as follows: ¹H-NMR (400 MHz, CD₂Cl₂): δ=7.71 (d, J=7.2 Hz, 1H), 7.41 (d, J=7.3 Hz, 1 H), 7.13 (m, 2 H), 6.96 (m, 1 H), 4.28 (s withSn satellites, 1 H), 2.21 (m, 1 H), 1.54 (m, 1 H), 1.45-0.65 (m, 39 H).³¹P-NMR (161.9 MHz, CD₂Cl₂): δ−11.3 ppm. The secondary isomer wasidentified as follows: ¹H-NMR (400 MHz, CD₂Cl₂): δ=7.6 (d, J=7.4 Hz, 1H), 7.46 (d, J=7.2 Hz, 1 H), 7.26 (t, J=7.5 Hz, 1 H), 7.1 (m, 1 H), 6.71(m, 1 H), 3.48 (m, 1 H), 2.21 (m, 1 H), 1.54 (m, 1 H), 1.45-0.65 (m, 39H). ³¹ P-NMR (161.9 MHz, CD₂Cl₂): d=−11.5 ppm.

Example 19 (Diisopropylphosphino-indenyl-zirconium trichloride, compound20)

A solution of 15.0 g of the compound 19 (0.029 mol) in 50 ml of toluenewas added dropwise to a suspension of 6.7 g (0.029 mol) of 99.9% pureZrCl₄ in 300 ml of toluene at −78° C. When the addition was complete,the reaction mixture was stirred at −30° C. for 0.5 hour and then at 0°C. for 4 hours. The yellow precipitate which formed was filtered off andwashed with toluene and hexane. The solids were dried in vacud, 8.8 g ofthe compound 20 (yield: 71%) remaining as a free-flowing yellow powder.The powder was further purified by removal of the remaining tincompounds by means of extraction with toluene fed under reflux over aperiod of 3 hours under 30 mm Hg and then with pentane over a period of2 hours in a Soxhlet extractor. Because of the insolubility of thecompound formed, no ¹H-NMR was obtained.

Example 20 (Diisopropylphosphino-dichloroboranyl-bridgedindenyl-cyclopentadienyl-zirconium dichloride, compound 21)

0.52 g (0.0012 mol) of the compound 20 and 30 ml of toluene wereintroduced into a Schlenk tube. 0.27 g (0.0012 mol) of the compound 2were added to this suspension in the course of 5 minutes. The yellowsuspension was stirred at room temperature for 3 hours, a slightlycloudy solution remaining. The precipitate was removed by filtration, apale yellow toluene solution remaining. After removal of the toluene invacuo, the product remained as a whitish solid in an amount of 0.47 g(yield: 87%). ¹H-NMR (400 MHz, CD₂Cl₂): δ=7.84 (pseudo dd, J=8.5, 0.8Hz, 1 H), 7.73 (d, J=8.8 Hz, 1 H), 7.5 (pseudo dt, J=7.8, 0.8 Hz, 1 H),7.38 (m, 2 H), 6.98 (m, 1 H), 6.67 (m, 1 H), 6.64 (m, 1 H), 6.54 (m, 1H), 6.29 (m, 1 H), 3.39 (septet, J=7.1 Hz, 1 H), 2.94 (m, 1 H), 1.68(dd, J_(H-P)=18.1 Hz, J=7.2 Hz, 3 H), 1.64 (dd, J_(H-P)=17.4, J=7.2 Hz,3 H), 1.45 (dd, J_(H-P)=15 Hz, J=7.2 Hz, 3 H), 1.33 (dd, J_(H-P)=14.6Hz, J=7.3 Hz, 3 H). ³¹P-NMR (161.9 MHz, CD₂Cl₂): δ=23.1 (br, m); ¹¹B-NMR(80 MHz, CD₂Cl₂): δ=−14.8 (br d, J=110 Hz).

Example 21 (Tributylstannyl-dimethylphosphino-indene, compound 22)

150 ml of ether were introduced into a round-bottomed flask whichcontained 5.5 g (0.047 mol) of indene; the mixture was cooled to −20° C.20.8 ml of a 2.3 molar solution of butyl-lithium in hexane (0.048 mol)were added to this solution in the course of 5 minutes, a yellowsolution being formed. After removal of the cooling bath, the solutionwas warmed to room temperature and subsequently stirred for 1 hour.After the reaction mixture had been cooled to −30° C., 4.6 g ofchlorodimethylphosphine (0.048 mol) in 30 ml of ether were added in thecourse of 20 minutes, a precipitate forming. After stirring at −20° C.for 2 hours, 20.8 ml of a 2.3 molar solution of butyl-lithium in hexane(0.048 mol) were added dropwise. When the addition was complete, thecooling bath was removed and the solution was warmed slowly to roomtemperature and subsequently stirred for 1.5 hours. After the suspensionhad been cooled to 0° C., 15.6 g of chlorotributyltin (0.048 mol) wereadded dropwise. The suspension formed was warmed to room temperature andstirred for 1.5 hours. The ether was removed in vacuo and the crudeproduct was dissolved again in hexane, the solution was filtered and thefiltrate was dried in vacuo, 17.4 g of the compound 22 (yield: 78%)remaining as a heavy yellow oil. ¹H-NMR (400 MHz, CD₂Cl₂): δ=7.67 (d,J=7.5 Hz, 1 H), 7.47 (d, J=7.4 Hz, 1 H), 7.18 (m, 2 H), 6.83 (m, 1 H),4.28 (s with Sn satellites, 1 H), 1.43-0.78 (m, 33 H). ³¹P-NMR (161.9MHz, CD₂Cl₂): δ=−61.6 ppm.

Example 22 (Dimethylphosphino-indenyl-zirconium trichloride, compound23)

A solution of 17.0 g of the compound 22 (0.037 mol) in 50 ml of toluenewas added to a suspension of 8.5 g (0.036 mol) of 99.9% pure ZrCl₄ in200 ml of toluene at −78° C. When the addition was complete, thereaction mixture was stirred at −30° C. for 0.5 hour and then at 0° C.for 4 hours. The yellow precipitate which formed was filtered off andwashed with toluene and hexane. The solids were dried in vacuo, 8.3 g ofthe compound 23 (yield: 61%) remaining as a free-flowing yellow powder.The powder was further purified by removal of the remaining tincompounds by means of extraction with toluene fed under reflux over aperiod of 3 hours under 30 mm Hg and then with pentane over a period of2 hours in a Soxhlet extractor, 7.2 g (yield: 53%) of the productremaining. Because of the insolubility of this compound, no ¹H-NMR wasobtained.

Example 23 (Dimethylphosphino-dichloroboranyl-bridgedindenyl-cyclopentadienyl-zirconium dichloride, compound 24)

30 ml of toluene and 0.55 g of the compound 23 (0.0015 mol) wereintroduced into a Schlenk tube. 0.31 g (0.0014 mol) of the compound 2were added to this suspension in the course of 5 minutes. The yellowsuspension was stirred at room temperature for 6.5 hours, a slightlycloudy solution remaining. The precipitate was removed by filtration, apale yellow toluene solution remaining. After removal of the toluene invacuo, the product remained as a whitish solid. After the product hadbeen washed with hexane and dried in vacuo, the compound 24 remained asa pale white solid (0.54 g; yield: 76%). ¹H-NMR (400 MHz, CD₂Cl₂):δ=7.84 (pseudo dd, J=7.4 Hz, 1.0 Hz, 1 H), 7.60 (m, 2 H), 7.51 (m, 1 H),7.38 (n, 1 H), 6.93 (m, 1 H), 6.71 (m, 1 H), 6.66 (m, 1 H), 6.49 (m, 1H), 6.30 (br s, 1 H), 2.11 (d J_(H-P)=11.9 Hz, 3 H), 1.94 (d,J_(H-P)=11.9 Hz, 3 H). ³¹P-NMR (161.9 MHz, CD₂Cl₂) −5.9 (br, m); ¹¹B-NMR(80 MHz, CD₂Cl₂): δ=−14.6 (br d, J_(B-P)=126 Hz).

Example 24 (2-Methylindene, compound 26)

38.7 g (0.29 mol) of 2-indanone and 300 ml of ether were introduced intoa round-bottomed flask. 96.7 ml of a 3.0 molar solution of CH₃MgI inether (0.29 mol), which was diluted with 150 ml of ether, wereintroduced into a second flask. Thereafter, the 2-indanone solution wasadded to the CH₃MgI solution via a cannula in an amount such that thereflux was maintained, a precipitate being formed. When the addition wascomplete, the suspension was fed under reflux for a further 4 hours andcooled to 0° C., after which 100 ml of a saturated solution of NH₄Clwere slowly added. The product was extracted with ether and dried overMgSO₄. After removal of the solvent in vacuo, 30.1 g (yield: 70%) of2-methyl-2-indanol (compound 25) were obtained as an oily solid. ¹H-NMR(400 MHz, CDCl₃): δ=7.15 (br m, 4 H), 3.01 (s, 2 H), 2.99 (s, 2 H), 1.5(s, 3 H); OH variable.

25.5 g (0.17 mol) of the compound 25, 3.2 g (0.017 mol) ofp-toluenesulfonic acid and 500 ml of hexane were introduced into around-bottomed flask with a Dean-Stark collecting vessel. Thissuspension was kept under reflux for 3 hours. After cooling, the hexanefraction was decanted from the insoluble products and the solvent wasremoved in vacuo, an oil remaining, which was then distilled in a shortdistillation column at 45° C. under 0.03 mbar, whereupon 15 g (yield:68%) of the compound 26 were obtained. ¹H-NMR (400 , CDCl₃): δ=7.33 (d,J=7.6 Hz, 1 H,), 7.21 (m, 2 H), 7.06 (pseudo d t, J=7.2, 1.4 Hz, 1 H),6.45 (br s, 1 H), 3.25 (s, 2 H), 2.12 (s, 3 H).

Reference is made to:

1. Morrison, H; Giacherio, D. J. Org. Chem. 1982. 47, 1058.

2. Ready, T. E.; Chien, J. C. W.; Rausch, M. D. J. Organom. Chem. 519,1996, 21.

3. Wilt, Pawlikowki, Wieczorek J. Org. Chem. 37, 1972, 824.

Example 25 (Tributylstannyl-diisopropylphosphino-2-methylindene,compound 27)

150 ml of ether were introduced into a round-bottomed flask whichcontained 5.08 g (0.039 mol) of 2-methylindene 26; the mixture wascooled to −20° C. 17.0 ml of a 2.3 molar solution of butyl-lithium inhexane (0.039 mol) were added to this solution in the course of 5minutes, a yellow solution being formed. After removal of the coolingbath, the solution was warmed to room temperature and subsequentlystirred for 1 hour. Thereafter, the reaction mixture was cooled to −20°C. and 5.8 g (0.039 mol) of chlorodiisopropylphosphine were added in thecourse of 5 minutes, a precipitate being formed. Thereafter, the coolingbath was removed and the reaction mixture was stirred at roomtemperature for 1 hour. After cooling to −20° C., 17.0 ml of a 2.3 molarsolution of butyl-lithium in hexane (0.039 mol) were added dropwise.When the addition was complete, the cooling bath was removed and thesolution was warmed slowly to room temperature and subsequently stirredfor 1.5 hours. After the suspension had been cooled to 0° C., 12.4 g(0.038 mol) of chlorodibutyltin were added dropwise. The suspensionformed was heated to room temperature and stirred for 1.5 hours. Theether was removed in vacuo and the crude product was dissolved again inhexane, the solution was filtered and the filtrate was dried in vacuo,20.4 g (yield: 98%) of the compound 27 remaining as a heavy yellow oil.Two isomers were identified by ³¹P NMR ³¹P-NMR (161.9 MHz, CD₂Cl₂):δ=−5.9 and −6.6 in a ratio of 2:1.

Example 26 (Diisopropylphosphino-2-methylindenyl-zirconium trichloride,compound 28)

A solution of 17.7 g (0.033 mol) of the compound 27 in 100 ml ofmethylene chloride was added to a suspension of 7.7 g (0.033 mol) of99.9% pure ZrCl₄ in 200 ml of methylene chloride at −25° C. in thecourse of 10 minutes. When the addition was complete, the reactionmixture was warmed slowly to 10° C. over a period of 3 hours, afterwhich a clear, orange-colored solution was formed. After 1 hour at roomtemperature, the solvent was removed in vacuo and the oil formed waswashed with 2×50 ml of hexane, whereupon an oily crude product (28) wasobtained, this being used directly for the preparation of the compound29. Because of the insolubility of this compound, no ¹H-NMR wasobtained.

Example 27 (Diisopropylphosphino-dichloroboranyl-bridged2-methylindenyl-cyclopentadienyl-zirconium dichloride, compound 29)

5.5 g (0.025 mol) of the compound 2 were introduced into around-bottomed flask, which contained 0.025 mol of the impure compound28 in 200 ml of toluene at 0° C., over a period of 5 minutes. After 1hour at 0° C., the stirring was ended and the soluble toluene fractionwas decanted from the oil formed. After removal of the toluene in vacuo,100 ml of hexane were added to the oily solid, 7.4 g (yield: 54%) of ayellow powder being formed with a purity of about 90%. The product wasfurther purified in a Soxhlet extraction apparatus with pentane fedunder reflux. The end product comprised a pale yellow powder. ¹H-NMR(400 MHz, CD₂Cl₂): δ=8.67 (br d, J=7.6 Hz, 1 H), 7.71 (m, 1 H), 7.35 (m,2 H), 6,62 (br s, 1 H), 6.54 (br s, 1 H), 6.47 (m, 1 H), 6.33 (m, 1 H),6.06 (br s, 1 H), 3.3 (br m, 1 H), 3.2 (br m, 1 H), 2.6 (s, 3 H), 1.78(dd, J=7.1 Hz, J_(H-P)=15.3 Hz, 3 H), 1.70 (dd, J=7.2 Hz, J_(H-P)=15.7Hz, 3 H). 1.57 (dd, J=7.1 Hz, J_(H-P)=15.3 Hz, 3 H), 1.12 (dd, J=7.1 Hz,J_(H-P)=14.0 Hz, 3H). ³¹P-NMR (161.9 MHz, CD₂Cl₂) 28.4 (br m); ¹¹B-NMR(80 MHz, CD₂Cl₂): δ=−14.3 (br d, J_(P-B)=106 Hz).

Example 28 Bis(trimethylsilyl)-(diphenylphosphino)-cyclopentadiene,compound 30)

76.6 ml of a 2.5 molar solution of butyl-lithium in hexane (0.19 mol)were added to a solution of the compound 1 (40.2 g; 0.19 mol) in 500 mlof ether at 0° C. in the course of 10 minutes. When the addition wascomplete, the bath was removed and the solution was stirred at roomtemperature for 1 hour. After cooling to 0° C., 42.2 g (0.19 mol) ofchlorodiphenylphosphine were added in the course of 10 minutes, afterwhich the bath was removed and the suspension was warmed to roomtemperature. After stirring at room temperature for 1 hour, the etherwas removed in vacuo and the product was dissolved again in hexane.After the salts had been filtered off, the hexane was removed in vacuo,69.1 g (yield: 91%) of the compound 30 remaining as an oil. ¹H-NMR (400MHz, CDCl₃): δ=7.45 (m, 4H), 7.35 (m, 6H), 6.8 (m, 1 H), 6.65 (m, 1 H),6.6 (m, 1H), 0 (s 18 H). ³¹P-NMR (161.9 MHz, CDCl₃): δ=−19.5 ppm.

Example 29 (Trimethylsilyl-diphenylphosphino-cyclopentadienyl-zirconiumtrichloride, compound 31)

A solution of the compound 30 (69.1 g, 0.175 mol) in 200 ml of methylenechloride was added to a suspension of 41.5 g (0.178 mol) of 99.9% pureZrcl₄ in 200 ml of methylene chloride via a cannula and the mixture wasstirred at room temperature for 8 hours. During this period, thesolution became cloudy. The solids were filtered off, washed with 2×20ml of toluene and then 2×20 ml of hexane and dried in vacuo. The productcomprised 35 g (yield: 39%) of a pale yellow powder. Because of theinsolubility of the product, no ¹H-NMR was obtained.

Example 30 (Diphenylphosphino-dichloroboranyl-bridgedtrimethylsilyl-cyclopentadienyl-cyclopentadienyl-zirconium dichloride,compound 32)

A solution of the compound 2 (2.6 g, 0.012 mol) was added to asuspension of the compound 31 (5.6 g, 0.011 mol) in 100 ml of toluene at0° C. After the mixture had been stirred at 0° C. for 5 hours, theyellow-brown solid was removed by filtration, a whitish solutionremaining. After removal of the toluene in vacuo and washing of thesolid which remained with pentane, the compound 32 remained as a highlyair-sensitive whitish powder (5.5 g; yield: 81%). ¹H-NMR (400 MHz,CD₂Cl₂): δ=7.8-7.5 (m, 10 H), 7.06 (m, 1 H), 6.92 (m, 1 H), 6.83 (m, 1H), 6.75 (m, 2 H) 6.68 (m, 1 H), 6.63 (m, 1 H), 0.26 (s, 9 H). ³¹P-NMR(161.9 MHz, CD₂Cl₂): δ=0 (br, m); ¹¹B-NMR (80 MHz, CD₂Cl₂): δ−16.3 (brd, J_(B-P)=82 Hz).

Example 31 (Diisopropylphosphino-cyclopentadienyl-lithium, compound 33)

50 ml of ether were introduced into a round-bottomed flask whichcontained 1.68 g (0.023 mol) of cyclopentadienyl-lithium. After thereaction flask had been cooled to −20° C., 3.6 g (0.023 mol) ofchlorodiisopropylphosphine were added dropwise. When the addition wascomplete, the cooling bath was warmed to 0° C. and the reaction mixturewas stirred for 1 hour. Thereafter, the ether was removed in vacuo, theproduct was dissolved in toluene and the solution was filtered. Afterthe frit had been rinsed through with 2×10 ml of toluene, the reactionmixture was cooled to −20° C. and 9.3 ml of a 2.5 molar solution ofbutyllithium in hexane (0.023 mol) were added, an orange-coloredsolution being formed. A small fraction was taken for NMR analyses and,after removal of the toluene in vacuo and washing of the oil formed withhexane, a pale yellow solid (13) was obtained.

¹H-NMR (400 MHz, THF): δ=5.89 (m, 2 H), 5.83 (br s, 2 H), 1.86 (m, 2 H),1.0-0.8 (m, 12 H). The main amount was used directly for the preparationof the compound 34.

Example 32 (Diisopropylphosphino-dimethylb oranyl-bridgedbis-cyclopentadienyl-titanium dichloride, compound 34)

A solution of 6.1 g (0.023 mol) of the compound 4 in 50 ml of toluenewas added to a toluene solution of the compound 33 (0.023 mol) from theabovementioned reaction at −78° C. After the mixture had been stirred at−78° C. for 30 minutes, the cooling bath was removed and the solutionwas subsequently stirred at room temperature for 2 hours. Thereafter,the solids were removed by filtration and the toluene was removed invacuo. Hexane was then added to the red oily product, a red powder beingformed, which was filtered off, washed with 2×20 ml of hexane and driedin vacuo, whereupon the compound 34 was formed as a red powder (5.95 g,yield, based on CpLi: 61%). ¹H-NMR (400 MHz, CD₂Cl₂): δ=6.96 (m, 2 H),6.94 (pseudo t, J=2.4 Hz, 2 H), 6.59 (m, 2 H), 6.42 (m, 2 H), 2.58 (m, 2H), 1.44 (dd, J=7.3 Hz, J_(H-P)=14.7 Hz, 6 H), 1.27 (dd, J=7.2 Hz,J_(H-P)=13.1 Hz, 6 H), 0.31 (d, J_(H-P)=16.4 Hz, 6 H). ³¹P-NMR (161.9MHz, CD₂Cl₂): δ=28.7 (br m); ¹¹B-NMR (80 MHz, CD₂Cl₂): δ=−29.7 (br m).

Example 33 (Dimethylphosphino-tributylstannyl-2-methylindene, compound35)

100 ml of ether were introduced into a round-bottomed flask whichcontained 6.76 g (0.052 mol) of 2-methylindene (compound 26); themixture was cooled to −20° C. 21 ml of a 2.5 molar solution ofbutyl-lithium in hexane (0.052 mol) were added to this solution in thecourse of 5 minutes, a yellow solution being formed. After removal ofthe cooling bath, the solution was warmed to room temperature andsubsequently stirred for 1 hour. After the reaction mixture had beencooled to −20° C., 5.0 g (0.052 mol) of chlorodimethylphosphine wereadded in the course of 5 minutes, a precipitate being formed. Thecooling bath was then removed and the reaction mixture was stirred atroom temperature for 1 hour. After cooling to −20° C., 21.0 ml of a 2.5molar solution of butyl-lithium in hexane (0.052. mol) were addeddropwise. When the addition was complete, the cooling bath was removed,after which the solution was warmed slowly to room temperature andstirred for 1.5 hours. After the suspension had been cooled to 0° C.,16.9 g (0.052 mol) of chlorotributyltin were added dropwise. Thesuspension formed was warmed to room temperature and stirred for 1.5hours. After removal of the ether in vacuo, the crude product wasdissolved again in hexane, the solution was filtered and the filtratewas dried in vacuo, 24.3 g (yield: 98%) of the compound 35 remaining asa heavy yellow oil. ³¹P-NMR (161.9 MHz, CD₂Cl₂): δ=−68.5 (s).

Example 34 (Dimethylphosphino-2-methylindenyl-zirconium trichloride,compound 36)

A solution of 17.4 g (0.036 mol of the compound 35 in 100 ml of toluenewas added to a suspension of 8.5 g (0.036 mol) of 99.9% pure ZrC1₄ in100 ml of toluene at 0° C. in the course of 10 minutes. When theaddition was complete, the reaction mixture was warmed slowly to 10° C.over a period of 1 hour and then stirred at room temperature for 6hours. The yellow precipitate was subsequently filtered off, washed with2×20 ml of toluene and 2×20 ml of hexane and dried in vacuo. The powderwas further purified by removal of the remaining tin compounds by meansof extraction with toluene fed under reflux over a period of 3 hoursunder 30 mm Hg and then with pentane over a period of 2 hours in aSoxhlet extractor, 5.8 g (yield: 41%) of the compound 36 remaining as aluminously yellow powder. Because of the insolubility of this compound,no ¹H-NMR was obtained.

Example 35 (Dimethylphosphino-dichloroboranyl-bridged2-methylindenyl-cyclopentadienyl-zirconium dichloride, compound 37)

2.7 g (0.012 mol) of the compound 2 were introduced into around-bottomed flask, which contained 4.8 g (0.012 mol) of the compound36 in 125 ml of toluene at room temperature, in the course of 5 minutes.After the mixture had been stirred for 7 hours, the dark yellow solidwas filtered off, washed with 2×20 ml of hexane and dried in vacuo, 5.5g (yield: 89%) of the compound 37 being obtained as a pale yellow solid.¹H-NMR (400 MHz, CD₂Cl₂): δ=8.39 (d, J=8.5 Hz, 1 H), 7.71 (m, 1 H), 7.4(m, 2 H), 6.64 (m, 2 H), 6.46 (pseudo q, J=5.3, 2.9 Hz, 1 H), 6.37 (m, 1H), 6.08 (m, 1 H), 2.51 (s, 3 H), 2.1 (d, J_(H-P)=12 Hz, 3 H), 2.0 (d,J_(H-P)=12 Hz, 3 H); ³¹P-NMR (161.9 MHz, CD₂Cl₂): δ=5.3 (br m); ¹¹B-NMR(80 MHz, CD₂Cl₂): δ=16.5 (br d, J_(B-P)=116 Hz).

Example 36 (Dicyclohexylboranylcyclopentadienyl-lithium, compound 39)

Reference is made to: Herberich, G. E.; Fischer, A. Organometallics1996, 15, 58.

40 ml of a 1 molar solution of chlorodicyclohexylborane in hexane (0.04mol) were added to 20 ml of cyclopentadienyl-sodium (2 M in THF; 0.04mol) in 100 ml of hexane at −78° C. After removal of the cooling bath,the reaction mixture was warmed to room temperature and stirred for 1hour. After filtration and removal of the solvent in vacuo, 9.1 g(yield: 94%) of the compound 38 remained as a yellow oil, which was useddirectly in the synthesis of the compound 39.

5.3 g (0.038 mol) of 2,2,6,6-tetramethylpiperidine were introduced intoa round-bottomed flask which contained 40 ml of ThF. After cooling to−20° C. and addition of 15 ml of a 2.5 molar solution of butyl-lithiumin hexane (0.038 mol), the mixture was stirred at −20° C. for 1 hour andthen cooled to −78° C. 9.1 g (0.038 mol) of the compound 38 in 20 ml ofhexane were added to this solution in the course of 10 minutes. Thecooling bath was removed and the solution was stirred at roomtemperature for 1 hour. After removal of the solvent in vacuo andaddition of hexane, the mixture was subsequently stirred for 2 hours, awhite suspension being formed, which was filtered, and the product wasdried in vacuo. 4.6 g (yield: 50%) of the compound 39 were formed as awhite powder. ¹¹B-NMR (80 MHz, THF): δ=43.9.

Example 37 (Diphenylphosphino-dicyclohexylboranyl-bridgedtrimethylsilyl-cyclopentadienyl-cyclopentadienyl-zirconium dichloride,compound 40)

After cooling a Schlenk flask which contained 1.4 g (0.0056 mol) of thecompound 39 and 2.9 g (0.0056 mol) of the compound 31 to −20° C., 100 mlof toluene were added. After removal of the bath, the suspension wasstirred at room temperature for 6 hours and then filtered. The solventwas removed in vacuo, an oily solid remaining, which was washed withhexane and filtered. After the solid had been dried in vacuo, 1.9 g(yield: 48%) of the compound 40 remained as a pink-colored solid. ¹H-NMR(400 MHz, CD₂Cl₂): δ=7.6-7.2 (br m, 10 H), 7.04 (br s, 1 H), 6.95 (m, 1H), 6.82 (m, 1 H), 6.76 (br s, 1 H), 6.66 (m, 1 H), 6.63 (m, 1 H), 6.52(m, 1 H), 1.6-1.1 (br m, 22 H), 0.26 (s, 9 H); ³¹P-NMR (161.9 MHz,CD₂Cl₂): δ=16.3; ¹¹B-NMR (80 MHz, CD₂Cl₂): δ=−13.8.

Example 38 (4,7-Dimethylindene, compound 41)

Reference is made to: Erker G. et al. Tetrahedron 1995, 51, 4347.

A 30% strength solution of 153 g (2.8 mol) of sodium methoxide inmethanol was diluted with 60 ml of methanol and cooled to 0° C. 34 g(0.52 mol) of cyclopentadiene were added to this solution. After 15minutes, 39 g (0.34 mol) of 2,5-hexanedione were added dropwise, afterwhich the cooling bath was removed and the reaction mixture was stirredat room temperature for 2 hours. 200 ml of water and 200 ml of etherwere then added. The ether layer was removed, washed with water andsodium chloride solution and then dried over Na₂SO₄. After removal ofthe solvent in vacuo and distillation at 65° C. under 0.1 bar, thecompound 41 remained as an orange-colored oil (40 g; yield: 81%). ¹H-NMR(400 MHz, CDCl₃): δ=7.35-7.27 (m, 2 H), 7.23 (d, J=7.6 Hz, 1 H), 6.82(m, 1 H), 3.51 (s, 2 H), 2.75 (s, 3H), 2.63 (s, 3 H).

Example 39 (Diisopropylphosphino-tributylstannyl-4,7-dimethylindene,compound 42)

100 ml of ether were introduced into a round-bottomed flask whichcontained 5.0 g (0.035 mol) of 4,7-dimethylindene (compound 41); themixture was cooled to −20° C. 14 ml of a 2.5 molar solution ofbutyl-lithium in hexane (0.035 mol) were added to this solution in thecourse of 5 minutes, a yellow solution being formed. After removal ofthe cooling bath, the solution was warmed to room temperature andsubsequently stirred for 1 hour. After the reaction mixture had beencooled to −20° C., 5.3 g (0.035 mol) of chlorodiisopropylphosphine wereadded in the course of 5 minutes, a precipitate being formed.Thereafter, the cooling bath was removed and the reaction mixture wasstirred at room temperature for 1 hour. After cooling to −20° C., 14.0ml of a 2.5 molar solution of butyl-lithium in hexane (0.035 mol) wereadded dropwise. When the addition was complete, the cooling bath wasremoved and the solution was warmed slowly to room temperature andstirred for 1.5 hours. After the suspension had been cooled to 0° C.,11.4 g of chlorotributyltin (0.035 mol) were added dropwise. Thesuspension formed was warmed to room temperature and stirred for 1.5hours. The ether was removed in vacuo and the crude product wasdissolved again in hexane, the solution was filtered and the filtratewas concentrated in vacuo, 16 g (yield: 83%) of the compound 42remaining as a heavy yellow oil. ³¹P-NMR (161.9 MHz, CD₂Cl₂): δ=−9 ppm.

Example 40 (Diisopropylphosphino-4,7-dimethylindenyl-zirconiumtrichloride, compound 43)

A solution of 16.0 g (0.029 mol) of the compound 42 in CH₂Cl₂ (100 ml)was added to a suspension of 6.4 g (0.029 mol) of 99.9% pure ZrCl₄ in100 ml of CH₂Cl₂ at −20° C. in the course of 10 minutes. When theaddition was complete, the reaction mixture was warmed slowly to roomtemperature over a period of two hours and then stirred at roomtemperature for a further 2 hours. Thereafter, the solids were removedby filtration and the solvent was removed in vacuo, the crude compound43 remaining as an oil which was used directly for the preparation ofthe compound 44.

Example 41 (Diisopropylphosphino-dichloroboranyl-bridged4,7-dimethylindenyl-cyclopentadienyl-zirconium dichloride, compound 44)

5.0 g (0.023 mol) of the compound 2 were introduced into around-bottomed flask, which contained 10.6 g (0.023 mol) of the compound43 in 125 ml of toluene at 0° C., in the course of 5 minutes. After themixture had been stirred at 0° C. for 1.5 hours, the cooling bath wasremoved and the suspension was stirred at room temperature for a further3 hours. Thereafter, the toluene-soluble fraction was decanted from theheavy oil which had formed during the reaction, and was concentrated todryness in vacuo, a heavy oil remaining. After addition of 100 ml ofhexane to this oil, the mixture was subsequently stirred and a darkyellow powder was filtered off and was dried in vacuo. After thisprocess, 6.3 g (yield: 48%) of the compound 44 remained as a dark yellowpowder. The product can be further purified by precipitation of a CH₂Cl₂solution of the compound 44 in a hydrocarbon solvent. ¹H-NMR (400 MHz,CD₂Cl₂): δ=8.03 (pseudo t, J=8.5 Hz, 1 H), 7.22 (d, J=7 Hz, 1 H), 7.08(d, J=7.1 Hz, 1 H), 7.02 (m, 1 H), 6.77 (m, 1 H), 6.70 (m, 1 H), 6.58(m, 1 H), 6.44 (br s, 1 H), 3.51 (m, 1 H), 2.82 (m, 1 H), 2.64 (s, 3 H),2.50 (s, 3 H), 1.77 (dd, J=7.2 Hz), J_(H-P)=16.3 Hz, 3 H) 1.69 (dd,J=7.1 Hz, J_(H-P)=15.2 Hz, 3 H), 1.58 (dd, J=7.1 Hz, J_(H-P)=15.5 Hz, 3H), 1.28 (dd, J=7.2 Hz, J_(H-P)=14.5 Hz, 3 H); ³¹P-NMR (161.9 MHz,CD₂Cl₂): δ=28.4 (br m); ¹¹B-NMR (80 MHz, CD₂Cl₂): δ=−15.3 (d,J_(P-B)=107 Hz).

Example 42 (Pyrrole-lithium, compound 45)

59 ml of a solution of butyl-lithium (2.5 molar in hexane, 0.148 mol)were added slowly to a solution of 9.9 g of pyrrole (0.148 mot) in 200ml of hexane at −20° C., a white solid being formed. The mixture wassubsequently stirred at room temperature for 2 hours and the solid wasisolated by filtration, washed twice with 20 ml of hexane each time anddried in vacuo. This process gave 6 g of the compound 45 (56% of thetheoretical yield).

¹H-NMR (400 MHF): δ=6.71 (s, 2H), 5.95 (s, 2H).

Example 43 (Dimethylboranyl-bridged cyclopentadienyl-pyrrole-titaniumdichloride, compound 46)

A solution of 1.34 g (0.005 mol) of the compound 4 in 20 ml of toluenewas added to 0.38 g (0.005 mol) of the compound 45 at −78° C. in thecourse of 5 minutes. The cooling bath was then removed and stirring wascontinued at room temperature for 2 hours. Thereafter, the red solidwhich had formed was filtered off; the yellow filtrate was discarded.The red solid was washed with toluene and dried in vacuo. 1.14 g with asmall content of LiCl were obtained.

¹H-NMR (400 MHz, THF): δ=6.89 (pseudo-t, J=2.3 Hz, 2 H), 6.64 (m, 2 H),6.59 (pseudo-t, J=2.35 Hz, 2 H), 5.73 (pseudo-t, J=1.7 Hz, 2 H), 0.06(s, 6 H). ¹¹B-NMR (80 MHz, THF): δ=−26 ppm.

Example 44 (1-Phenyl-2,3,4,5-tetramethyl-phosphol, compound 47)

In accordance with Organometallics 7 (1988), 921, a solution of 11.7 g(0.216 mol) of 2-butine in 150 ml of CH₂Cl₂ was slowly added to 15.3 g(0.115 mol) of AlCl₃ in CH₂Cl₂ (0° C.; 30 minutes). The mixture wassubsequently stirred at 0° C. for 45 minutes, the cooling bath was thenremoved and the mixture was subsequently stirred for a further hour.Thereafter, the solution was cooled to −50° C. and a solution of 21.4 g(0.12 mol) of phenyl-dichlorophosphine in CH₂Cl₂ was added in the courseof 20 minutes. The cooling bath was then removed and the dark redsolution was subsequently stirred for one hour and then added to asolution of 27 g (0.13 mol) of tributylphosphine in 100 ml of CH₂Cl₂ at−30° C. The red color disappeared immediately; a yellow solutionremained. When the addition had ended, the solvent was removed in vacuo;a thick yellow oil remained. The oil was taken up in hexane and washedwith saturated aqueous NaHCO₃ solution and H₂O under an Ar atmosphere.After drying over MgSO₄, the hexane was removed in vacuo. 18.2 gremained as a clear oil (yield 78%). ¹H-NMR (400 MHz, CDCl₃): δ=7.3 (m,5H), 2.0 (m, 12H), ³¹P-NMR (161.9 MHz, CDCl₃): δ=16.8 ppm.

Example 45 (Lithium-2,3,4,5-tetramethyl-phosphol, compound 48)

In accordance with Organometallics 7 (1988), 921, 0.52 g (0.074 mol) oflithium was added to a solution of 7 g (0.032 mol) of the compound 47 in150 ml of tetrahydrofuran (THF) and the mixture was stirred overnight.The resulting red solution was filtered through a frit to removeresidual solids and the filtrate was cooled to 0° C. Thereafter, asolution of 1.45 g (0.01 mol) of AlCl₃ in 20 ml of THF was addeddropwise and the solution was brought to room temperature. An aliquotamount was removed for analysis and the remaining solution was useddirectly for the preparation of the compound 49. ³¹P-NMR (161.9 MHz,THF): δ=63.7 ppm.

Example 46(Dimethylboranyl-cyclopentadienyl-tetramethylphosphol-titaniumdichloride, compound 49)

The THF solution from Example 45 with 1.46 g (0.01 mol) of the compound48 was introduced into a round-bottomed flask; THF was removed in vacuo.After addition of toluene and cooling to −78° C., a solution of 2.6 g(0.01 mol) of the compound 44 in 20 ml of toluene was slowly added,while stirring, a red suspension being formed. When the addition hadended, the suspension was brought to room temperature and subsequentlystirred for 1 hour. After solid which had remained undissolved wasfiltered off, the toluene was removed in vacuo; hexane was added to theoily solid which remained. The solid which remained undissolved was alsofiltered off from the hexane solution and the solution was storedovernight at −20° C. After the hexane had been decanted off, 0.5 g of agreen solid which was identified as compound 49 (yield 14%) wasobtained. ¹H-NMR (200 MHz, CD₂Cl₂): δ=6.64 (m, 2H), 6.57 (m, 21), 2.11(d, J_(H-P)=10 Hz, 6H), 2.09 (s, 6H), 0.87 (d, J_(H-P)=5.3 HZ, 6 1).³¹P-NMR (161.9 MHz, THF): =δ96.5 ppm, ¹¹B-NMR (80 MHz, CD₂Cl₂): δ=39(br, m) ppm.

Example 47 (Diphenylphosphino-dichloroboranyl-bridgedbis(indenyl)-zirconium dichloride, compound 50)

0.011 mol of trimethylsilyl-dichloroboranyl-indene was added to asuspension of 0.012 mol of diphenylphosphino-indenyl-zirconiumtrichloride in 150 ml of toluene at room temperature. The reactionmixture was then stirred at 75° C. for 1 hour. After cooling andfiltration, 150 ml of hexane was added to the clear orange-coloredsolution, after which a heavy red oil and a pale yellow precipitateformed; the precipitate was filtered off, washed with hexane and driedin vacuo. The pale yellow solid was identified as the pure meso compoundby ¹H-NMR spectroscopy. The filtrate with the red oil was concentratedto 30 ml and added dropwise to 200 ml of hexane, after which a secondpale yellow precipitate formed, which was filtered off and dried invacuo. This product was identified as the pure rac isomer with the aidof X-ray structure analysis. Crystals suitable for this purpose werecultured by slow diffusion of hexane into a saturated CH₂Cl₂ solution atthe ambient temperature. The donor-acceptor bond P→B has a length of2.02 Å. The yield was 40% and the meso/rac ratio was 1:1. If thereaction mixture was stirred for 5 hours (instead of 1 hour), at 75° C.,an increased amount of the desired rac isomer was obtained; the meso/racratio was 1:4. At the same time, the overall yield raised slightly from40% to 45%.

Elemental analysis: 56.05% C (theoretical 55.90%), 4.35% H (4.38%)

Spectrum meso isomer: ¹H-NMR (400 MHz, CD₂Cl₂, room temperature RT):8.01 ppm (1H, d, 8.8 Hz); 7.8-7.0 ppm (several overlapping multiplets,28H); 6.94 ppm (1H, t, 3.3 Hz); 6.77 ppm (1H, d, 3.44 Hz); 6.31 ppm (1H,d, 8.7 Hz), ³¹P-NMR (161.9 MHz CD₂Cl₂): 5.6 ppm. ¹¹B-NMR (80.2 MHzCD₂Cl₂): −17.0 ppm (72 Hz).

Spectrum rac isomer: ¹H-NMR (400 MHz, CD₂Cl₂, RT): 8.39 ppm (1H, d, 8.5Hz); 7.68-7.05 ppm (27H, various overlapping multiplets); 6.65 ppm (1H,d, 2.9 Hz), 6.59 ppm (1H, t, 3.5 Hz); 6.51 ppm (1H, t, 2.8 Hz); 6.40 ppm(1H, d, 3.5 Hz) ³¹P-NMR (161.9 MHz, CD₂Cl₂): 8.1 ppm. ¹¹B-NMR (80.2 MHz,CD₂Cl₂): −14.0 ppm (J_(P-B) 74 Hz).

Examples 48 to 50 (Dialkylphosphino-dichloroboranyl-bridgedbis(indenyl)-zirconium dichloride; alkyl=i-propyl=compound 51;ethyl=compound 52; methyl=compound 53)

0.016 mol of trimethylsilyl-dichloroboranyl-indene in 50 ml of toluenewas added to a suspension of 0.0157 mol ofdialkylphosphinoindenyl-zirconium trichloride in 250 ml of toluene atroom temperature. The reaction mixture was then heated for a few hours,while stirring. After cooling and filtration, 300 ml of hexane wereadded to the clear orange-colored solution, after which a heavy red oiland a clear yellow solution formed. Separation of the meso and racisomers was achieved by fractional crystallization from toluene/hexanesolutions.

Characterization of the compounds (NMR spectra in CD₂Cl₂ at RT; ¹H-NMR:400 MHz ³¹P-NMR: 161.9 MHz, ¹¹B-NMR: 80.2 MHz):

rac compound 51 (i-Pr):

¹H-NMR: 8.41 ppm (1 H, d, 9.0 Hz); 8.31 ppm (1 H, d, 8.4 Hz); 7.84 ppm(1 H, d, 8.5 Hz); 7.64 to 7.24 ppm (6 H, various overlappingmultiplets); 6.70 ppm (2 H, m); 6.60 ppm (1 H, m): 3.78 ppm (1 H, m,P(CH(CH₃)₂)₂); 3.21 ppm (1 H, m P(CH(CH₃)₂)₂); 1.81 ppm (6 H, m, P(CH(CH₃)₂)₂); 1.72 ppm (3 H, dd, P(CH(CH ₃)₂)₂, 14.9 Hz, 7.3 Hz); 1.32 ppm (3H, dd, P(CH(CH ₃)₂)₂, 14.1 Hz, 7.4 Hz). ³¹P-NMR: 22.7 ppm. ¹¹B-NMR:−14.1 ppm (100 Hz).

Elemental analysis: 49.4% C (theoretical 48.9%), 4.6% H (4.4%).

meso compound 52 (Et):

¹H-NMR: 7.83 ppm (1 H, d, 9.0 Hz); 7.76 ppm (1 H, m); 7.63 ppm (1 H, d,7.2 Hz); 7.47 ppm (1 H, d, 8.5 Hz); 7.33 ppm (2 H, m); 7.20-7.03 ppm (4H, various overlapping multiplets); 6.76 ppm (2 H, m); 2.68 ppm (2 H, m,P(CH ₂CH₃)₂); 2.44 ppm (2 H, m, P(CH ₂CH₃)₂); 1.62 ppm (3 H, m, P(CH₂(CH₃)₂); 1.27 ppm (3 H, m, P(CH₂CH ₃)₂). ³¹P-NMR: 7.1 ppm. ¹¹B-NMR: −15.8ppm (100 Hz).

rac compound 52 (Et):

¹H-NMR: 8.28 ppm (1H, d, 8.6 Hz); 8.10 ppm (1 H, d, 8.6 Hz); 7.62 ppm (1H, d, 8.4 Hz); 7.46 ppm (1H, d, 8.5 Hz); 7.41 to 7.10 ppm (4 H, variousoverlapping multiplets); 6.81 ppm (1 H, m); 6.47 ppm (2 H, m): 6.38 ppm(1 H, d, 3.4 Hz), 2.68 ppm (2 H, m P(CH ₂CH₃)₂); 2.35 ppm (2 H, m, P(CH₂CH₃)₂); 1.30 ppm (6 H, m, P(CH₂(CH₃)₂). ³¹P-NMR: 12.3 ppm. ¹¹B-NMR:−15.7 ppm.

Elemental analysis: 47.6% C (theoretical 47.1%), 4.3% H (4.0%).

meso compound 53 (Me):

¹H-NMR: 7.84 ppm (1 H, d); 7.75 ppm (1 H, d, 8.2 Hz); 7.68 ppm (1 H, d,7.7 Hz); 7.51 ppm (1H, d, 8.5 Hz); 7.40 to 7.10 ppm (6 H, variousoverlapping multiplets); 6.77 ppm (2 H, br); 2.13 ppm (3 H, P(CH ₃)₂, d,11.8 Hz); 1.92 ppm (3 H, P(CH ₃)₂, d, 11.8 Hz). ³¹P-NMR: 8.4 ppm.¹¹B-NMR: −16.1 ppm (103 Hz).

rac compound 53 (Me):

¹H-NMR: 8.21 ppm (1 H, d, 8.7 Hz); 8.15 ppm (1 H, d, 8.6 Hz); 7.63 ppm(1 H, d, 8.5 Hz); 7.44 to 7.07 ppm (6 H, various overlappingmultiplets); 6.40 ppm (3 H, br); 2.03 ppm (3 H, d, P(CH ₃)₂, 11.9 Hz);1.98 ppm (3 H, d, P(CH ₃)₂, 11.6 Hz). ³¹P-NMR: −1.5 ppm. ¹¹B-NMR: −16.0ppm (119 Hz).

Example 51 (1,3-Bis(trimethylsilyl)-2-methylindene, compound 54)

500 ml of hexane and 70 ml of butyllithium (as a 2.5 molar solution inhexane) were introduced into a 1000 ml flask. 0.175 mol of2-methylindene was added dropwise to this at ambient temperature; themixture was stirred for a further 10 hours. 0.18 mol of trimethylsilylchloride was then added dropwise at room temperature; the mixture wasstirred for a further 10 hours. LiCl was filtered off and 70 ml ofbutyllithium (as a 2.5 molar solution in hexane) were added to the clearfiltrate. After further stirring for 10 hours, 0.18 mol oftrimethylsilyl chloride was again added and the mixture was stirred fora further 10 hours. LiCl was filtered off and the solvent was removed invacuo. Compound 54 remained as a colorless oil. Yield: 85% of thetheoretical yield.

¹H-NMR (CD₂Cl₂): 7.51 ppm (1 H, d, 7.7 Hz); 7.38 ppm (1 H, d, 7.5 Hz);7.19 ppm (1 H, t, 7.4 Hz); 7.08 ppm (1 H, t, 7.3 Hz); 3.54 ppm (1H, s);2.32 ppm (3 H, s); 0.41 ppm (9 H, s, Si(CH ₃)₃); 0.0 ppm (9 H, s, Si(CH₃)₃).

Example 52 (Trimethylsilyl-dichloroboranyl-2-methylindene, compound 55)

0.096 mol of the compound 54 was introduced into a 250 ml flask equippedwith a dry ice condenser (−30° C.). 0.096 mol of BC₃ was then added andthe mixture was stirred at ambient temperature for 3 hours and at 55° C.for 6 hours. The by-product (CH₃)₃SiCl was removed; a brown oil remainedas the crude product. Distillation from cold trap to cold trap gave thecompound 55 in a yield of 75% as a tacky solid.

¹H-NMR (CD₂Cl₂): 8.09 ppm (1 H, d, 7.9 Hz); 7.37 ppm (1 H, d, 7.6 Hz);7.26 ppm (1 H, t, 7.5 Hz); 7.16 ppm (1 H, t, 7.5 Hz); 3.89 ppm (1H, s);2.61 ppm (3 H, s); 0.0 ppm (9 H, s, Si(CH ₃)₃). ¹¹B-NMR (CD₂Cl₂): 31.9ppm.

Example 53 (Tributylstannyl-diethylphosphino-2-rmethylindene; compound56)

The procedure was analogous to Example 7.

Example 54 (Diethylphosphino-2-methylindenyl-zirconium trichloride,compound 57)

The procedure was analogous to Example 8, but instead of toluene, CH₂Cl₂was used as the solvent. The reaction temperature was 25° C. Thepurification was carried out by Soxhlet extraction with CH₂Cl₂. Compound57 was obtained as an insoluble yellow solid in 78% of the theoreticalyield.

Example 55 ((C₂H₅)₂P-BCl₂-bridged bis(2-methylindenyl)-zirconiumdichloride, compound 58)

0.019 mol of compound 55 in 50 ml of toluene was added to a suspensionof 0.019 mol of compound 57 in 350 ml of toluene at room temperature.

The reaction mixture was then heated to 80° C. and stirred for 24 hours.After cooling and filtration, 300 ml of hexane were added to the clear,orange-colored solution, after which a heavy orange-colored oil and aclear yellow solution formed. Concentration and cooling to −25° C. gavethe compound rac-58 as a pale yellow powder.

¹H-NMR: 8.14 ppm (1 H, d, 8.6 Hz); 7.96 ppm (1 H, d, 8.9 Hz); 7.47 to7.05 ppm (6 H, various overlapping multiplets); 6.53 ppm (1H, d, 1.9Hz); 6.47 ppm (1 H, s); 3.0 ppm to 2.55 ppm (4 H, various overlappingmultiplets, P(CH ₂CH₃)₂); 2.21 ppm (3 H, s, CH ₃); 2.08 ppm (3 H, s, CH₃); 1.44 ppm (3 H, m, P(CH₂CH ₃)₂), 1.07 ppm (3 H, m, P(CH₂CH ₃)₂).³¹P-NMR: 21.4 ppm. ¹¹B-NMR: −14.7 ppm.

Example 56 (Ethene-propene copolymerization)

100 ml of dry toluene, which had been distilled under inert gas, and 10g of propene were initially introduced into a dry, oxygen-free 300 mlV4A autoclave. The autoclave was heated at 40° C., the catalyst wasadded under pressure by means of a pressure sluice and the internalpressure was immediately adjusted to a constant 10 bar with ethene. Thecatalyst used was 5×10⁻⁷ mol of [(cp)Ph₂PBMe₂(cp)TiCl₂], which had beenpreformed (activated) with 5×10⁻³ mol MAO at room temperature for 15minutes. The internal temperature rose to 60° C. The polymerization wasinterrupted after 30 minutes. After working up (precipitation andwashing) with ethanouhydrochloric acid and ethanol, 0.9 g of an E-Pcopolymer was isolated.

Catalyst activity: about 3.5 tonnes per mole of catalyst and hour

IR analysis: 42% by weight of propene, 58% by weight of ethene

DSC analysis: partly crystalline copolymer,

Melting peak: T_(m1) =−31°, T_(m2) =106° C.

Glass transition temperature: T_(g) =−55° C.

Limiting viscosity in ortho-dichlorobenzene at 140° C.:

[η]=2.88 dl/g

Example 57 (Ethene-propene copolymerization)

The procedure was as in the above example, the internal temperature ofthe autoclave being adjusted to 60° C. and the internal pressure beingadjusted by 6 bar to a constant 11 bar with ethene. The catalyst usedwas 5×10⁻⁷ mol of [((CH₃)₃Si-cp)Ph₂PBCl₂(Cp)ZrCl₂], which had beenpreformed with 5×10⁻³ mol of MAO at room temperature for 15 minutes. Theinternal temperature rose from 60° to 78° C.

Polymer yield after 30 minutes: 9.8 g. Catalyst activity: 39.2 tonnes ofcopolymer per mole of catalyst and hour IR analysis: 31% by weight ofpropene, 69% by weight of ethene DSC analysis: partly crystallinecopolymer Melting peak: −2°, +62°, 102° C. Glass transition temperature:T_(g) = −55° C. Limiting viscosity in ortho-dichlorobenzene [η] = 0.88dl/g at 140° C.:

In a comparison experiment at 40° C. (exothermic up to about 50° C.), acompletely amorphous copolymer with a propene content of 46% by weightand a [η] value of 0.87 dl/g formed.

Example 58 (Ethene-propene copolymerization)

The procedure was as in the above example, [r-(ind)i-Pr₂PBCl₂(ind)ZrCl₂]being used as the D/A metallocene, with the same catalyst and cocatalystamounts as there, and the pressure at 80° being increased by 2 bar to aconstant 8.5 bar with ethene. The internal temperature rose to 82° C.

Catalyst activity: 4.4 tonnes of copolymer per mole of catalyst and hour

Catalyst activity: 4.4 tonnes of copolymer per mole of catalyst and hourDSC analysis: partly crystalline copolymer T_(m) = +37° C. T_(g) = −49°C. Limiting viscosity in ortho-dichlorobenzene [η] = 1.41 dl/g at 140°C.:

Example 59 (Propene polymerization)

About 1 mol of propene was initially introduced into a dry, oxygen-free300 ml V4A steel autoclave and the bulk polymerization was started at20° C. by addition of catalyst by means of a pressure sluice. Thecatalyst used was 1×10⁻⁶ mol of [(Me₃Si-cp)Ph₂PBCl₂(Cp)ZrCl₂] and 1×10⁻²mol of MAO in 9 ml of toluene.

The internal temperature rose from 20° to 24° C. After one hour, 3.2 gof a rubber-like polypropylene were isolated after working up withethanol/hydrochloric acid and drying.

Catalyst activity: 3.2 tonnes per mole · h DSC: amorphous PP, Tg = −4°C. GPC (polystyrene calibration): M_(w) = 143 kg/mol M_(n) = 28 kg/molLimiting viscosity (o-Cl₂-benzene, 140° C.) η = 0.66 dl/g NMR (triadanalysis) 37% isotactic 42% atactic 21% syndiotactic

Example 60 (Propene polymerization)

A thoroughly heated 300 ml V4A steel autoclave was charged with 100 mlof dry, oxygen-free toluene and 0.5 ml of a 1 molartriisobutylaluminum/toluene solution. About 1 mol of propene was thentransferred into the autoclave. 1 ml of a chlorobenzene solution whichcomprised 4×10⁻⁶ mol of dimethylaniliniumtetrakis(pentafluoro-phenyl)borate was added to 3.1 ml of a toluenesolution of the catalyst, which had been preformed at RT for 30 minutesand comprised 1×10⁻⁶ mol of rac[(2-Me-ind)Et₂PBCl₂(2-Me-ind)ZrCl₂] and0.1 mmol of triisobutyl-aluminum (TiBA), in a pressure sluice and themixture was topped up to 5 ml with toluene. After the catalyst solutionhad been transferred into the autoclave under pressure, the internaltemperature rose from 20° C. to 48° C., in spite of external coolingwith dry ice/acetone.

20 minutes after addition of the catalyst, the polymerization wasinterrupted and the contents of the autoclave were extracted by stirringin 500 ml of ethanol and 50 ml of concentrated aqueous hydrochloric acidfor 2 hours. The white polypropylene powder was then isolated byfiltration, washed with ethanol and dried at 115° C.

Polymer yield: 11.6 g

Catalyst activity: 34.8 tonnes of i-PP per mole of catalyst and hour

The DSC measurement gave, in the 2nd heating up, a melting temperatureT_(m)=−155° C.

The NMR measurement gave an isotacticity index I.I.=88%

The limiting viscosity, measured in o-dichlorobenzene at 140° C., was[η]=3.60 dl/g, corresponding to a molar mass M_(visc.)=798 kg/mol.

In further experiments at increasing temperature, an increasingproportion of atactic sequences was observed. This is visible in the DSCmeasurement by an increasingly pronounced glass transition stage in thetemperature range from 0 to −20° C.

What is claimed is:
 1. A process for the preparation of a thermoplasticelastomer by (co)polymerization of monomers from the group consisting ofC₂-C₈-α-olefins, C₄-C₁₅-diolefins, mono- or dihalogenatedC₄-C₁₅-diolefins, vinyl esters (meth)acrylates and styrene in the bulk,solution, slurry or gas phase in the presence of organometalliccatalysts, which can be activated by cocatalysts, which comprisesemploying as the organometallic catalyst a metallocene compound or πcompound of the formula

in which CpI and CpII are two identical or different carbanions having acyclopentadienyl-containing structure, in which one to all the H atomscan be replaced by identical or different radicals from the groupconsisting of linear or branch C₁-C₂₀-alkyl, which can bemonosubstituted to completely substituted by halogen, mono- totrisubstituted by phenyl or mono- to trisubstituted by vinyl,C₆-C₁₂-aryl, halogenoaryl having 6 to 12 C atoms, organometallicsubstituents, including silyl, trimethylsilyl or ferrocenyl, or one ortwo can be replaced by D and A, D denotes a donor atom, which canadditionally carry substituents and has at least one free electron pairin its bond state, A denotes an acceptor atom, which can additionallycarry substituents and has an empty orbital capable of accenting a pairof electrons in its bond state, wherein D and A are linked by areversible coordinate bond such that the donor group assumes a positivecharge and the acceptor group assumes a negative charge, M represents atransition metal of sub-group III, IV, V or VI of the Periodic Table ofthe elements, including the lanthanides and actinides, X denotes oneanion equivalent and n denotes the number zero, one, two, three or four,depending on the charge of M, or a π complex compound, and a metallocenecompound of the formula

in which πI and πII represent different charged or electrically neutralπ systems which can be condensed with one or two unsaturated orsaturated five- or six-membered rings, D denotes a donor atom, which isa substituent of πI or part of the π system of πI and has at least onefree electron pair in its bond state, A denotes an acceptor atom, whichis a substituent of πII or part of the π system of πII and has an emptyorbital capable of accepting a pair of electrons in its bond state,wherein D and A are linked by a reversible coordinate bond such that thedonor group assumes a positive charge and the acceptor group assumes anegative charge, and where at least one of D and A is part of theassociated π system, wherein D and A in their turn can carrysubstituents, wherein each π system and each fused-on ring system cancontain one or more D or A or D and A and wherein πI and πII in thenon-fused or in the fused form, one to all the H atoms of the π systemindependently of one another can be replaced by identical or differentradicals from the group consisting of linear or branched C₁-C₂₀-alkyl,which can be monosubstituted to completely substituted by halogen, mono-to trisubstituted by phenyl and mono- to trisubstituted by vinyl,C₆-C₁₂-aryl, halogenoaryl having 6 to 12 C atoms, organometalsubstituents, including silyl, trimethylsilyl or ferrocenyl, or one ortwo can be replaced by D and A, so that the reversible coordinate D→Abond is formed (i) between D and A, which are both parts of the π systemor the fused-on ring system, or (ii) of which D and A is part of the πsystem and in each case the other is a substituent of the non-fused πsystem or the fused-on ring system, or (iii) both D and A are suchsubstituents, wherein the case of (iii) at least one additional D or Aor both is (are) parts of the π system or of the fused-on ring system, Mand X have the above meanings and n denotes the number zero, one, two,three or four, depending on the charges of M and those of π-I and π-II.2. The process as claimed in claim 1, wherein the metallocene compoundor the π complex compound is employed as the catalyst in an amount of10¹ to 10¹² mol of monomers per mole of metallocene or π complexcompound.
 3. The process as claimed in claim 1, wherein solvents areused in said process, said solvents selected from the group consistingof aromatic hydrocarbons, saturated hydrocarbons, aromatichalohydrocarbons and saturated halohydrocarbons.
 4. The process asclaimed in claim 1, wherein, in the metallocene compound, the carbanionsCpI and CpII or the π system πI denote a cyclopentadienyl skeleton fromthe group consisting of cyclopentadiene, substituted cyclopentadiene,indene, substituted indene, fluorene and substituted fluorene, in which1 to 4 substituents from the group consisting of C₁-C₂₀-alkyl,C₁-C₂₀-alkoxy, halogen, C₆-C₁₂-aryl, halogenophenyl, D and A, wherein Dand, are present, per cyclopentadiene or fused-on benzene ring, it beingpossible for fused-on aromatic rings to be partly or completelyhydrogenated.
 5. The process as claimed in claim 1, wherein, in themetallocene compound, elements selected from the group consisting of N,P, As, Sb, Bi, O, S, Se, Te, F, Cl, Br and I, are present as donor atomsD.
 6. The process as claimed in claim 1, wherein, in the metallocenecompound, elements selected from the group consisting of B, Al, Ga, Inand Tl, are present as acceptor atoms A.
 7. The process as claimed inclaim 1, wherein, in the metallocene compound or π complex compound,donor-acceptor bridges selected from the group consisting of N→B, N→Al,P→B, P→Al, O→B, O→Al, Cl→B, Cl→Al, C═O→B, C═O→Al are present.
 8. Theprocess as claimed in claim 1, wherein, in the metallocene compound, Mrepresents Sc, Y, La, Sm, Nd, Lu, Ti, Zr, Hf, Th, V, Nb, Ta or Cr,preferably.
 9. The process as claimed in claim 1, wherein themetallocene compound or π complex compound is employed as a catalystsystem together with an aluminoxane, a borane or borate and, optionally,further cocatalysts and/or metal-alkyls.
 10. The process as claimed inclaim 1, wherein rearrangement products of said metallocene compound orπ complex compound with self-activation, with which, after opening ofthe D/A bond, the acceptor atom A bonds an X ligand to form azwitterionic metallocene complex structure or π complex structure, wherea positive charge is generated in the transition metal M and a negativecharge is generated in the acceptor atom A, and where a further X ligandrepresents H or substituted or unsubstituted C, in the bond of which tothe transition metal M the olefin insertion takes place for thepolymerization, preferably 2 X ligands being linked to a chelate ligand,are employed.
 11. The process as claimed in claim 1, wherein in said πcomplex compound D is part of the ring of the associated π system. 12.The process as claimed in claim 1, wherein a reaction product of theformulae (XI) (a-d) of an ionizing agent with a metallocene compound orπ complex according to formula (I) or (XIII)

in which Anion represents the entire bulky, poorly coordinating anionand Base represents a Lewis base, is employed.
 13. The process asclaimed in claim 1, wherein said thermoplastic elastomer isthermoplastic-elastomeric propylene.
 14. The process according to claim5, wherein, in the metallocene compound, elements selected from thegroup consisting of N, P, O and S are present as donor atoms D.
 15. Theprocess according to claim 6, wherein, in the metallocene compound,elements selected from the group consisting of B, Al, and Ga, arepresent as acceptor atoms A.
 16. The process according to claim 8,wherein, in the metallocene compound, M represents Ti, Zr, Hf, V, Nb orTa.